Functional filler and resin composition containing same

ABSTRACT

The present invention provides a functional filler which is excellent in dispersibility or interaction with polylactic acid as a matrix polymer and can improve heat resistance, moldability and mechanical strength of the polylactic acid; and a resin composition containing the functional filler. The functional filler of the present invention is characterized in including a raw material filler and polylactic acid, wherein a surface or end the raw material filler is modified by the polylactic acid.

TECHNICAL FIELD

The present invention relates to a functional filler, a functionalfiller composition containing the functional filler, a resin compositioncontaining the functional filler, production methods thereof, and amolded body including the resin composition.

BACKGROUND ART

Polylactic acid is one kind of biodegradable polymer, and can beproduced using reproducible plant resources, food residuals fromeveryday life, old papers or the like and without using petroleumresources. Further, since the waste thereof is degraded in nature, it isless likely that the disposal of the waste becomes a problem as withconventional plastic products. Therefore, polylactic acid is expected toplay a large role in solving problems of resources, energy andenvironment from the present to the future.

Specifically, in the case that polylactic acid is used for agriculturalmaterials or the like, it is not necessary to collect them after use.Further, in case that polylactic acid is used in a packing container ofa packed lunch at a convenience store or food, the container can bedisposed as garbage without separating leftovers or food after use.Therefore, since polylactic acid allows the rationalization of amaterial cycle or transportation by utilizing characteristics of abiodegradable resin originated in plants, polylactic acid can contributelargely to saving labor and saving energy. Further, also in the case ofusing polylactic acid in living bodies, since its degradation productsare lactic acid, carbon dioxide and water, which are harmless to a humanbody, polylactic acid can be used as a medical material or the like.

However, while polylactic acid is excellent in transparency as PS resinand PET resin, there is a problem of being inferior in heat resistance,moldability and mechanical strength such as impact property. Suchproperties have been a problem on attempting to expand a broad range ofuse.

In order to improve the heat resistance, moldability and mechanicalstrength such as impact property of polylactic acid, a method isattempted, in which fillers such as silica is blended with polylacticacid. Such a technique is described in Japanese publication of patentapplication Nos. 2005-200600, 2005-112456 and 2004-224990.

DISCLOSURE OF THE INVENTION

As described above, the technique in which filler such as silica isblended with polylactic acid to improve heat resistance and the like isknown. However, the dispersibility in polylactic acid as a matrixpolymer and the interaction with polylactic acid of filler such assilica which is used conventionally are insufficient. Therefore, theimprovement has not been achieved so that the heat resistance,moldability and mechanical strength such as impact property can bear thepractical demand even when these fillers are blended with polylacticacid.

The problem to be solved by the present invention is to provide afunctional filler which is excellent in dispersibility in polylacticacid as a matrix polymer, in interaction with polylactic acid, and inimprovement effect of heat resistance, moldability and mechanicalstrength such as impact property of polylactic acid, and a functionalfiller composition and a resin composition containing the functionalfiller. Further, an object of the present invention is also to provide amethod of producing the functional filler and the like, and a moldedbody including the above-described resin composition.

In order to solve the above-described problems, the present inventorshave made eager investigations, particularly on a filler to be added topolylactic acid composition. As a result, the inventors found that afiller is modified with a substituent which interacts with molecules ofpolylactic acid as a matrix polymer by utilizing the properties ofstrong interaction of an optically active polylactic acid oligomer orpolymer, such as poly-D-lactic acid, with a polylactic oligomer orpolymer which is an optical isomer, such as poly-L-lactic acid, to solvethe above problems. More specifically, since such a functional fillerinteracts with multiple polylactic acid molecules and has a so-calledaction effect for crosslinking multiple polylactic acid molecules, heatresistance, strength and the like of the polylactic acid can beimproved.

The functional filler of the present invention is characterized incomprising a raw material filler and polylactic acid, wherein a surfaceor end the raw material filler is modified by the polylactic acid.

The functional filler composition of the present invention ischaracterized in comprising the above functional filler and non-bondedpolylactic acid produced during production of the above functionalfiller.

The resin composition of the present invention is characterized incomprising the above functional filler and polylactic acid as a matrixpolymer, wherein the polylactic acid as a matrix polymer at least partlyinteracts with the polylactic acid modifying the surface or end of thefunctional filler.

The method for producing the above functional filler according to thepresent invention is characterized in comprising steps of: mixing lacticacid solution and/or lactide solution or lactic acid melt and/or lactidemelt with the raw material filler; and polymerizing the lactic acidand/or lactide to modify the surface or end of the raw material fillerwith polylactic acid.

The method for producing the functional filler composition according tothe present invention is characterized in comprising steps of: using anexcessive amount of lactic acid and/or lactide to the raw materialfiller during mixing lactic acid solution and/or a lactide solution orlactic acid melt and/or lactide melt with the raw material filler; andpolymerizing the lactic acid and/or lactide to modify the surface or endof the raw material filler with polylactic acid.

The method for producing the resin composition according to the presentinvention is characterized in comprising steps of: mixing lactic acidand/or lactide solution or lactic acid melt and/or lactide melt with theraw material filler; polymerizing the lactic acid and/or lactide tomodify the surface or end of the raw material filler with polylacticacid to obtain the functional filler; and mixing the functional fillerwith the polylactic acid as a matrix polymer at least partly interactingwith polylactic acid modifying the surface or end of the functionalfiller.

The molded body of the present invention is characterized in comprisingthe above resin composition.

According to the present invention, the following effects can beexerted. The filler surface is modified with polylactic acid whichinteracts with polylactic acid as a matrix polymer, to largely improvethe dispersibility of the filler in the matrix polymer. Further,polylactic acid on the filler surface and the matrix polymer form astereo complex, to improve the heat resistance and strength of theobtained resin composition. Furthermore, since the stereo complexfunctions as a nucleating agent, the crystallization speed of the resincomposition becomes fast; and the molding speed, the stretchingtemperature and the stretching ratio can be improved. Therefore,physical properties and moldability of the obtained molded product canbe improved, and thus applications can be expanded. In addition, sincethe obtained molded body is reinforced with fillers, the strengththereof is high. With the characteristics of the functional filler ofthe present invention described above, in the case of performing atreatment such as stretching and molding on the resin composition of thepresent invention in a solid state or a melt state, uniform stretchingand molding can be performed due to a small crystal size, a fillereffect, a high melt viscosity or the like, and stability duringproduction of a stretched product or a molded product and quality andperformance of the product can be improved.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view showing an outline of the functional fillerof the present invention. In the figure, a reference numeral 1represents a raw material filler, and a reference numeral 2 representspolylactic acid bonded on the filler surface.

FIG. 2 is IR data of the functional filler of the present invention andraw material filler thereof.

FIG. 3 is NMR data of the functional filler of the present invention andraw material filler thereof.

BEST MODE FOR CARRYING OUT THE INVENTION

The functional filler of the present invention includes a raw materialfiller and polylactic acid, wherein the surface or end of the rawmaterial filler is modified. FIG. 1 is a schematic view showing anoutline of the functional filler of the present invention. Hereinafter,the polylactic acid which modifies the surface or end of the filler maybe sometimes referred to as “polylactic acid (A)”.

Conventionally, a method, in which the surface of silica is modifiedwith a silane-coupling agent to increase compatibility with polylacticacid, has been used for silica generally used as a filler of polylacticacid, in order to increase dispersibility in an aliphatic ester such aspolylactic acid. However, the effect thereof has not been sufficient. Onthe other hand, in the present invention, polylactic acid which isfurther excellent in compatibility with polylactic acid than the silicacoupling agent is introduced on the surface of the filler, thereby toextremely increase the dispersibility and the interaction in thepolylactic acid.

In more detail, an optically active lactic acid oligomer or polymer suchas poly-D-lactic acid strongly interacts with a lactic acid oligomer orpolymer which is an optically isomer such as poly-L-lactic acid.Therefore, when, for example, a mixture of poly-D-lactic acid andpoly-L-lactic acid is used as a matrix polymer, since the matrixpolymers interact with each other, heat resistance or the like ofpolylactic acid composition material is considered to be improved.However, in such an embodiment, the probability that one poly-D-lacticacid interacts with one poly-L-lactic acid is considered to be high, andthe probability that one poly-D-lactic acid interacts with two or morepoly-L-lactic acids is considered to be extremely low. On the otherhand, the functional filler of the present invention can be bonded tomultiple matrix polymer molecules depending on the number of polylacticacids bonded to the surface or end of the filler, and therefore a stereocomplex is formed. As a result, it becomes possible to remarkablyimprove the heat resistance or the like of the polylactic acidcomposition material.

Polylactic acid of which at least part interacts with a matrix polymermolecule may be selected as polylactic acid (A). For example, in casethat the matrix polymer molecule is poly-D-lactic acid, polylactic acid(A) which at least partly has an oligomer or polymer part includingL-lactic acid is used, and poly-L-lactic acid having mainly L-lacticacid is preferably used. Further, when a block of D-lactic acid isreferred to X and a block of L-lactic acid is referred to Y, forexample, in case that polylactic acid as a matrix polymer is a blockcopolymer of X—Y—X, polylactic acid (A) is preferably made to be a blockcopolymer of Y—X—Y. Furthermore, for example, in case that polylacticacid as a matrix polymer is a mixture of poly-D-lactic acid andpoly-L-lactic acid, polylactic acid (A) may be also made to be a mixtureof poly-D-lactic acid and poly-L-lactic acid. Further, if at least apart of polylactic acid (A) can interact with a matrix polymer molecule,the polylactic acid (A) may be a random copolymer of D-lactic acid andL-lactic acid. In any cases, polylactic acid (A) can be selectedappropriately depending on the optical characteristics of the matrixpolymer.

In the present invention, a “poly-D-lactic acid” and “poly-L-lacticacid” are not limited to ones constituted with only D-lactic acid andL-lactic acid, respectively, and may each mainly include D-lactic acidand L-lactic acid, respectively, as a main constituent. Here, “as a mainconstituent” means that the content of D-lactic acid or L-lactic acid inlactic acid constituting a “poly-D-lactic acid” or “poly-L-lactic acid”,respectively, is preferably 80% by weight or more, more preferably 85%by weight or more, and further preferably 90% by weight or more.Components other than D-lactic acid or L-lactic acid in poly-D-lacticacid or poly-L-lactic acid may be each optical isomer, that is L-lacticacid for poly-D-lactic acid, and may be other components which can bepolymerized with lactic acid. Examples of other components which can bepolymerized with lactic acid include a divalent or more alcoholcompound, a divalent or more carboxylic acid compound, and aring-opening polymerizable compound such as cyclic lactone, cyclic etherand cyclic lactam.

Polylactic acid shows high crystallinity and is excellent in heatresistance and mechanical properties, when the ratio of L-lactic acid orD-lactic acid is high, that is when optical purity thereof is high. Onthe other hand, a copolymer with a relatively high ratio of L-lacticacid in poly-D-lactic acid or of D-lactic acid in poly-L-lactic acid islow in crystallinity or is amorphous, additionally low in heatresistance and low in mechanical property. Therefore, polylactic acidwith high optical purity is preferable as the polylactic acid of thepresent invention. Homo-poly-D-lactic acid or homo-poly-L-lactic acidconsisting of substantially 100% of optically active lactic acid ispreferably used as polylactic acid (A).

Polylactic acid (A) preferably has a number-average molecular weight of100 to 1,000,000. When the molecular weight is 100 or more, thedispersibility of the function filler according to the present inventionin the matrix polymer can be secured sufficiently. On the other hand,when the molecular weight is 1,000,000 or less, the stereo complex canbe formed sufficiently. Moreover, the number-average molecular weightcan be measured using a GPC, i.e. gel permeation chromatography,measurement as described later.

The functional filler of the present invention is one in which thesurface or end of the raw material filler is modified with polylacticacid (A). This modification is performed by chemically and/or physicallybonding polylactic acid (A) to the surface or end of the raw materialfiller. Here, example of the chemical bond includes an ester bond formedwith a hydroxy group of the terminal lactic acid molecule of thepolylactic acid, an ester bond and an amide bond formed with a carboxylgroup of the terminal lactic acid molecule, or the like. Further,example of the physical bond includes an ion bond, a hydrogen bond, andthe like. Therefore, when the raw material filler is one which has afunctional group capable of being chemically and/or physically bonded toa carboxyl group, a hydroxy group or a carbonyl group on the surface orend, the filler can be easily modified with polylactic acid (A). Exampleof such a functional group includes hydrophilic functional groups suchas an amino group, a hydroxy group, a carboxyl group and an epoxy group.In case that the raw material filler does not have these hydrophilicfunctional groups on surface or end thereof, the hydrophilic functionalgroup may be introduced using a known method. Further, the carboxylgroup or the like may be active-esterified in order to increasereactivity.

The raw material filler may be any of an inorganic stick-shaped filler,a layer-shaped filler, a particle-shaped filler and sol solutionsthereof, and an organic compound, i.e. organic filler, which dissolvesor disperses homogenously with the polymer matrix can be used. Further,metal alkoxides which are raw materials of the inorganic filler can bealso used.

The stick-shaped filler, that is a fibrous filler or a needle-shapedfiller, is preferably one which has the highest aspect ratio, i.e.length/diameter or diameter/length, and can largely improve mechanicalcharacteristics of the resin composition. Specific example thereofincludes an inorganic fibrous and needle-shaped filler such as glassfiber, asbestos fiber, carbon fiber including a fibrous new carbon suchas carbon nanotube, a needle-shaped new carbon and a sphere-shaped newcarbon such as fullerene, graphite fiber, metal fiber, stick-shapedhydroxyapatite, potassium titanate whisker, aluminum borate whisker,magnesium whisker, silicon whisker, wollastonite; sepiolite, slag fiber,Zonolite, Ellestadite, boehmite, plaster fiber, silica fiber, aluminafiber, silica and alumina fiber, zirconia fiber, boron nitride fiber andboron fiber; and an organic fibrous filler such as polyester fiber,nylon fiber, acrylic fiber, cellulose filer, acetate fiber, aramidefiber, kenaf fiber, lamy, cotton, jute, hemp, sisal, flax, linen, silk,manila hemp, wood pulp, old paper and wool.

A layer-shaped filler or a plate-shaped filler is inferior in impactstrength compared with a particle-shaped filler, however, has a higheraspect ratio than that of the particle-shaped filler, and therefore thelayer-shaped or plate-shaped filler has advantages such as largeimprovement effect of rigidity and excellent dimensional stability.Specific example includes natural and synthetic smectite or the like,and more specifically clay such as Kunipia (registered trademark) Pmanufactured by Kunimine Industries Co., Ltd., and smectone;plate-shaped alumina, talc, mica, cerisite, glass flakes, various metalfoils, black lead, plate-shaped calcium carbonate, plate-shaped aluminumhydroxide, plate-shaped magnesium hydroxide or the like, as a material.

Sphere-shaped and amorphous particle-shaped fillers are ones having anaspect ratio close to 1. Specific example includes ones havinghydroxyapatite, calcium carbonate, silica, mesoporous silica, zirconia,alumina, Y—PSZ, spinel, talc, mullite, cordierite, silicon carbide,aluminum nitride, hematite, cobalt blue, cobalt violet, cobalt green,magnetite, Mn—Zn ferrite, Ni—Zn ferrite, yttrium oxide, cerium oxide,samarium oxide, lanthanum oxide, tantalum oxide, terbium oxide, europiumoxide, neodymium oxide, zinc oxide, titanium oxide, magnesium fluoride,tin oxide, antimony-containing tin oxide (ATO), tin-containing indiumoxide, barium titanate, PT, PZT, PLZT and clay as a material; variouscrushed ore products; various beads; various balloons and the like.

Example of the sol solution includes a silica sol solution, a boehmitesol solution or the like, manufactured by Nissan Chemical Industries,Ltd., Fuso Chemical Co., Ltd., and Kawaken Fine Chemicals Co., Ltd.

Example of the metal alkoxides includes silicon-based alkoxides,titanium-based alkoxides, aluminum-based alkoxides, zirconium-basedalkoxides, tin-based alkoxides, germanium-based alkoxides, rare earthelement-based alkoxides, and mixture and/or complex alkoxide thereof.

Example of the silicon-based alkoxides includes tetraalkoxysilane havingan alkoxy group having 1 to 5 carbon atoms, such as tetraethoxysilane;methyltrialkoxysilane such as methyltriethoxysilane;phenyltrialkoxysilane such as phenyltriethoxysilane;dimethyldialkoxysilane such as dimethyldiethoxysilane;diphenyldialkoxysilane such as diphenyldimethoxysilane anddiphenylsilanediol; vinyltrialkoxysilane such as SILA-ACE (registeredtrademark) 5210 and 5220 manufactured by Chisso Corporation;N-(2-aminoethyl)-3-aminopropylmethyldialkoxysilane such as SILA-ACE S310manufactured by Chisso Corporation;N-(2-aminoethyl)-3-aminopropyltrialkoxysilane such as SILA-ACE S320manufactured by Chisso Corporation; 3-aminopropyltrialkoxysilane such asSILA-ACE S330 and S360 manufactured by Chisso Corporation;3-glycidoxypropyltrialkoxysilane such as SILA-ACE S510 manufactured byChisso Corporation; 3-glycidoxypropylmethyldialkoxysilane such asSILA-ACE 5520 manufactured by Chisso Corporation;2-(3,4-epoxycyclohexyl)ethyltrialkoxysilane such as SILA-ACE 5530manufactured by Chisso Corporation; 3-chloropropylmethyldialkoxysilanesuch as SILA-ACE S610 manufactured by Chisso Corporation;3-chloropropyltrialkoxysilane such as SILA-ACE 5620 manufactured byChisso Corporation; 3-methacryloxypropyltrialkoxysilane such as SILA-ACE5710 manufactured by Chisso Corporation; 3-mercaptopropyltrialkoxysilanesuch as SILA-ACE S810 manufactured by Chisso Corporation;N-(1,3-dimethylbutylidene)-3-(trialkoxysilyl)-1-propaneamine such asSILA-ACE S340 manufactured by Chisso Corporation;N-[2-(vinylbenzylamino)ethyl]-3-aminopropyltrialkoxysilane hydrochloridesuch as SILA-ACE S350 manufactured by Chisso Corporation;N,N′-bis[3-(trialkoxysilyl)propyl]ethylenediamine such as SILA-ACEXS1003 manufactured by Chisso Corporation; an oligomer of an amino-basedsilane coupling agent such as SILA-ACE Oligomer MS3201, MS3202, MS3301and MS3302 manufactured by Chisso Corporation; an oligomer of anepoxy-based silane coupling agent such as SILA-ACE Oligomer MS5101 andMS5102 manufactured by Chisso Corporation; a terminal-hydrogenatedpolydimethylsiloxane such as SILAPLANE (registered trademark) FM-1111,SILAPLANE FM-1121 and SILAPLANE FM-1125 manufactured by ChissoCorporation; a terminal-vinylated polydimethylsiloxane such as SILAPLANEFM-2231 manufactured by Chisso Corporation; a methacryloxylgroup-terminated polydimethylpolysiloxane such as SILAPLANE FM-7711,SILAPLANE FM-7721, SILAPLANE FM-7725, SILAPLANE FM-0711, SILAPLANEFM-0721, SILAPLANE FM-0725, SILAPLANE TM-0701 and SILAPLANE TM-0701Tmanufactured by Chisso Corporation; a terminal-hydroxylatedpolydimethylsiloxane such as SILAPLANE FM-0411, SILAPLANE FM-0421,SILAPLANE FM-0425, SILAPLANE DA-11, SILAPLANE DA-21 and SILAPLANE DA-25manufactured by Chisso Corporation; a terminal-epoxylatedpolydimethylsiloxane such as SILAPLANE FM-0511, SILAPLANE FM-0521 andSILAPLANE FM-0525 manufactured by Chisso Corporation; aterminal-carboxylated polydimethylsiloxane such as SILAPLANE FM-0611,SILAPLANE FM-0621 and SILAPLANE FM-0625 manufactured by ChissoCorporation; polysilsesquioxane such polymethylsilsesquioxane (100%methyl), polymethyl-hydridesilsesquioxane (90% methyl-10% hydride),polyphenylsilsesquioxane (100% phenyl), polyphenyl-methylsilsesquioxane(90% phenyl-10% methyl), phenylsilsesquioxane-dimethylsiloxane copolymer(70% phenyl-30% dimethyl), polyphenyl-propylsilsesquioxane (70% phenyland 30% propyl), polyphenyl-vinylsilsesquioxane (90% phenyl-10% vinyl),a T7 cube with polycyclohexylsilsesquioxanesilanol reactivity>90%, a T7cube with polycyclohexylsilsesquioxanesilanol reactivity>95%, a T8 cubefor polycyclopentylsilsesquioxane (H substitution) hydrosilylation, apolycyclopentylsilsesquioxane (methacryloxy substitution) polymerizableT8 cube, a polycyclopentylsilsesquioxane (all H substitution) T8 cube,poly(2-chloroethyl)silsesquioxane, a T8 cube, andpoly(2-chloroethyl)silsesquioxane.

Example of the titanium-based alkoxides includes tetraalkoxy titaniumhaving an alkoxy group having 1 to 10 carbon atoms, such as tetraethoxytitanium; and titanium di-n-butoxide such as bis-2,4-pentanedionate.

Example of the aluminum-based alkoxides includes aluminum propoxide;aluminum dialkoxy diketonate such as aluminum di-sec-butoxideethylacetoacetate; aluminum alkoxy bis-diketonate such asaluminum-sec-butoxide bis(ethylacetoacetate); aluminum tri-diketonatesuch as aluminum tri-2,4-pentanedionate; aluminum carboxylate such asaluminum acetate and aluminum acrylate.

Example of the zirconium-based alkoxides includes zirconium hydroxide;tetraalkoxy zirconium having an alkoxy group having 1 to 10 carbonatoms, such as tetra-n-propoxy zirconium; zirconium trialkoxy diketonatesuch as zirconium methacryloxy ethylacetoacetate tri-n-propoxide;zirconium dialkoxy diketonate such as zirconiumdi-iso-propoxide(bis-2,2,6,6-tetramethyl-3,5-heptadionate); zirconiumtetraketonate such as zirconium tetra-2,4-pentanedionate; and zirconiumcarboxylate such as zirconyl dimethacrylate and zirconyl propionate.

Example of hafnium-based alkoxides includes tetraalkoxy hafnium havingan alkoxy group having 1 to 10 carbon atoms, such as tetra-n-butylhafnium; hafnium tetraketonate such as hafnium tetra-2,4-pentanedionate;and hafnium dialkoxy diketonate such as hafniumdi-n-butoxide(bis-2,4-pentadionate).

Example of yttrium-based alkoxides includes trialkoxy yttrium having analkoxy group having 1 to 10 carbon atoms such as yttriumtriisopropoxide; yttrium tri-diketonate such as yttriumtri-2,4-pentadionate; and aluminum carboxylate such as yttrium acetateand yttrium acrylate.

Example of the organic filler includes divalent or more alcohol, phenol,carboxylic acid, amine, epoxy, latex or the like.

Example of the divalent or more alcohol or phenol includes divalentalcohol or phenol such as; ethylene glycol; diethylene glycol;triethylene glycol; polyethylene glycol and polypropylene glycol havinga molecular weight of 200 to 35,000; 1,3-propanediol; 1,4-butanediol;1,5-pentanediol; 1,6-hexanediol; 1,7-heptanediol; 1,8-octanediol;1,9-nonanediol; 1,10-decanediol; 1,11-undecanediol; 1,12-dodecanediol;1,4-dibenzyl alcohol; 1,4-dihydroxybenzene; 1,3-dihydroxybenzene;4,4′-dihydroxybiphenyl; 2,2′-dihydroxybiphenyl; 4-hydroxyphenethylalcohol; 3-(4-hydroxyphenyl)-1-propanol; hydroquinonebis(2-hydroxyethyl)ether; 4,4′-isopropylidenebis[2-(2,6-dibromophenoxy)ethanol]; 2-2(2-hydroxyetoxy)phenol;trans-9,10-dihydro-9,10-ethanoanthracene-11,12-dimethanol;2-hydroxyphenethylalcohol; 3-hydroxyphenethylalcohol;1-phenyl-1,2-ethanediol; 2-benzyloxy-1,3-propanediol;3-phenoxy-1,2-propanediol; 1,5-dihydroxy-1,2,3,4-tetrahydronaphthalene;2,2-biphenyldimethanol; 3,5-dihydroxybenzylalcohol; hydrobenzoin;α-naphtolbenzein; benzopinacol; 2-hydroxybenzylalcohol;1,2-benzenedimethanol; 2,2-(1,2-phenylenedioxy)diethanol;3-hydroxybenzylalcohol; 1,3-benzenedimethanol;α,α,α′,α′-tetramethyl-1,3-benzenedimethanol;α,α,α′,α′-tetrakis(trifluoromethyl)-1,3-benzenedimethanol;1,4-benzenedimethanol; 3-aminobenzylalcohol;α,α,α′,α′-tetramethyl-1,4-benzenedimethanol;α,α,α′,α′-tetrakis(trifluoromethyl)-1,4-benzenedimethanol hydrate;phenylhydroquinone; 2,2′,3,3′,5,5′,6,6′-octafluoro-4,4′-biphenolhydrate; bis(4-hydroxyphenyl)methane; bisphenol A; bisphenol P;bisphenol M; 4,4′-(hexafluoroisoproplidene)diphenol;2,2-bis(4-hydroxy-3-methylphenyl)propane;1,1,1-tris(4-hydroxyphenyl)ethane; hexestrol; tetrafluorohydroquinone;1,1′-bi-2-naphthol; 4,4′-(9-fluorenylidene)diphenol;2,7-dihydroxyfluorene; 4,4′-(1,3-adamantanezyl)diphenol;N,N′-bis(2-hydroxyethyl)oxixamide; 1,5-dihydroxynaphthalene;1,6-dihydroxynaphthalene; 1,7-dihydroxynaphthalene;2,3-dihydroxynaphthalene; 2,6-dihydroxynaphthalene;2,7-dihydroxynaphthalene; polycarbonatediol having a molecular weight of250 to 10,000, such as UC-CARB100, UH-CARB50, UH-CARB100, UH-CARB200,UH-CARB300, UM-CARB90(1/1) and UM-CARB90(3/1) manufactured by UbeIndustries, Ltd.; polyetherdiol having a molecular weight of 250 to10,000, such as polytetrahydrofran; polyesterdiol having a molecularweight of 250 to 10,000; polycaptolactonediol having a molecular weightof 250 to 10,000; hydroquinone;4,8-bis(hydroxymethyl)-tricyclo[5.2.1.0(2,6)]decane;1,4-cyclohexanemethanol; 4,4′-isopropylidenedicyclohexanol;1,5-decalinediol; 2,2,3,3,4,4,5,5-octafluoro-1,6-hexanediol;2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9-hexadecafluoro-1,10-decanediol; bothterminals hydroxylated polydimethyl(phenyl)siloxane such as SILAPLANEFM-4411, SILAPLANE FM-4421 and SILAPLANE FM-4425 manufactured by ChissoCorporation; trimethylolethane; trivalent alcohol or phenol such as;trimethylolethane; trimethylolpropane;2-(hydroxymethyl)-1,3-propanediol,2-ethyl-2-(hydroxymethyl)-1,3-propanediol;1,1,1-tris(hydroxymethyl)ethane; 1,2,4-butanetriol; glycerol;1,3,5-trimethylolbenzene; 1,2,4-trihydroxybenzene;1,3,5-trihydroxybenzene; pyrogallol; 1,3,5-tris(2-hydroxyethyl)cyanuricacid; tetravalent alcohol or phenol; such as pentaerythritol;di(trimethylolpropane); DL-xylose; D-xylose; L-xylose;1,1,1,5,5,5-hexafluoro-2,2,4,4-pentanetetrol;1,2,4,5-tetramethylolbenzene; calix[4]arene; pentavalent alcohol such asL-mannose and xylitol; alcohol or phenol of hexavalent or more such asdipentaerythritol, tripentaerythritol, inositol, α-cyclodextrin,β-cyclodextrin, γ-cyclodextrin, calix[6]arene and calyx[8]arene; or thelike.

Example of carboxylic acid of divalent or more includes divalentcarboxylic acid such as terephthalic acid; succinic acid; glutaric acid;adipic acid; 1,10-decanedicarboxylic acid; perfluoroadipic acid;perfluorosuberic acid; perfluorosebacic acid; 1,3-adamantanediaceticacid; 1,3-adamantanedicarboxylic acid; 1,4-cyclohexanedicarboxylic acid;trans-1,4-cyclohexanedicarboxylic acid; 1,3-cyclohexanedicarboxylicacid; 1,2-cyclohexanecarboxylic acid; and both terminals carboxylatedpolydimethyl(phenyl)siloxane such as SILAPLANE FM-6611, SILAPLANEFM-6621 and SILAPLANE FM-6625 manufactured by Chisso Corporation;trivalent carboxylic acid such as trimesic acid; 1,2,3-benzenecarboxylicacid; 1,3,5-cyclohexanetricarboxylic acid; and1,3,5-trimethyl-1,3,5-cyclohaxanetricarboxylic acid; tetravalent or morecarboxylic acid such as 1,2,4,5-benzenetetracarboxylic acid;cyclobutanetetracarboxylic acid; and 1,2,3,4,5,6-hexacarboxylic acid.

Example of amine of divalent or more includes ethylenediamine;1,3-diaminopropane; 1,2-diaminopropane; 1,4-diaminobutane;1,5-diaminopentane; hexamethylenediamine; 1,7-diaminoheptane;1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane;1,11-diaminoundecane; 1,12-diaminododecane; 4,4′-diaminobenzanilide;bis(hexamethylene)triamine; 4-(aminomethyl)-1,8-octanediamine;tris(2-aminoethylamine);5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine;5-amino-1,3,3-trimethylcyclohexanemethylamine;4,4′-methylenebis(2-methylcyclohexylamine);1,3-cyclohexanebis(methylamine); 4,4′-methylenebis(cyclohexylamine);4,4′-ethylenedianiline; 3,3′-methylenedianiline;4,4′-methylenedianiline;4,4′-methylenebis(3-chloro-2,6-dimethylaniline); 4,4′-oxydianiline;4,4′-ethylenedi-m-toluidine; o-tolidine; tetramethylbenzidine;1,4-phenylenediamine; 1,2-phenylenediamine; 1,3-phenylenediamine; afunctional resin monomer manufactured by Mitsui Chemicals, Inc., such asAPB, APB-N, Bisaniline-P, Bisaniline-M and NBDA; 2,3-diaminotoluene;4-chloro-1,2-phenylenediamine; 4,5-dichloro-1,2-phenylenediamine;3,4-diaminotoluene; 4-methoxy-1,2-phenylenediamine; 2,6-diaminotoluene;4,4′-diaminooctafluorobiphenyl; 3,3-diaminobenzidine;4,5-dimethyl-1,2-phenylenediamine; 2,4-diaminotoluene;3,5-diaminobenzylalcohol; 1,2,4,5-benzenetetramine;4,4′-(hexafluoroisoproplidene)dianiline; 3,3′-dimethoxybenzidine;pararosaniline base; 3,3′-dimethylnaphthydine; 1,5-diaminonaphthalene;2,7-diaminofluorene; 1,8-diaminonaphthalene; 9,10-diaminophenanthrene;2,3-diaminonaphthalene; 3,7-diamino-2-methoxyfluorene; melamine;2,4,6-triaminopyrimidine; 2-dimethyl-1,3-propanediamine; spermidine;spermine; diethylenetriamine; trans-1,4-diaminocyclohexane; bothterminals aminated polydimethyl(phenyl)siloxane such as SILAPLANEFM-3311, SILAPLANE FM-3321 and SILAPLANE FM-3325 manufactured by ChissoCorporation; or the like.

Example of divalent or more epoxy includes a bisphenol A type epoxyresin; brominated bisphenol A epoxy resin; orthocresol novolac typeepoxy resin; alicyclic epoxy resin; DCPD epoxy resin; polyphenol typeepoxy resin such as a brominated novolac type, phenolnovolac type andbisphenyl type epoxy resin; polyglycidylamine type epoxy resin such as1,3,5-tris(2,3-epoxypropyl)isocyanurate; alcohol type epoxy resin; estertype epoxy resin; or the like. The above epoxy compounds are describedin p. 1126 to p. 1135 in “Chemical Products of 14705” published by TheChemical Daily Co., Ltd. Example of other divalent or more epoxyincludes both terminals epoxylated polydimethyl(phenyl)siloxane such asSILAPLANE FM-5511, SILAPLANE FM-5521 and SILAPLANE FM-5525 manufacturedby Chisso Corporation.

Latex includes products of JSR Cooperation, Nippon A & L, Inc., ZeonCooperation or the like, and example includes trade name PYRATEX andNipol series.

One kind of the raw material filler may be used alone, or two or morekinds may be mixed and used.

An example of the especially preferable raw material filler includes atleast one selected from a group consisting of pentaerythritol, trimesicacid, dipentaerythritol, polytetrahydrofran, myo-inositol,polyethyleneglycol, tetraethoxysilane, methyltriethoxysilane,1,4-phenylenediamine, hexamethylenediamine, 4,4′-biphenol,1,3,5-tris(2-hydroxyethyl)cyanuric acid, N,N′-bis(hydroxyethyl)oxamideand bisphenol. The effect of the functional filler having these rawmaterial fillers as constitutional components is proven in Examplesdescribed later.

The functional filler according to the present invention is preferablymodified with 0.01 part by mass or more of polylactic acid (A) per 100parts by mass of the raw material filler. In case that the polylacticacid (A) is 0.01 part by mass or more, the dispersibility in polylacticacid as a matrix polymer can be secured sufficiently, and theimprovement effect of heat resistance, moldability and mechanicalstrength of the obtained resin composition is sufficient. The amount ofthe polylactic acid (A) is more preferably 0.1 part by mass or more perpart by mass of the raw material filler, and more preferably 0.2 to 2000parts by mass.

The hydroxy group or the carboxyl group of the end of the polylacticacid which modifies the surface or end of the raw material filler may beprotected. More specifically, the hydroxy group or the carboxyl group ispreferably esterified, urethanized or etherified. In particular,esterification is preferable. With such protection, thermal stability ofthe functional filler, the resin composition and the like of the presentinvention can be improved.

Sulfonic acid esterification and phosphoric acid esterification are alsoincluded in the above-described esterification other than carboxylicacid esterification. Example of phosphonic acid esters includes amonoester, diester and triester.

The above-described hydroxy group can be protected by esterification,urethanization or etherification. The esterification can be performedusing derivative such as organic acid: R—CO₂H and acid anhydride thereofor the like. The urethanization can be performed using carbamic acidderivative such as RNHCOCL or the like. The etherification can beperformed using halogen compound such as R—Cl or the like. Further, theabove-described carboxyl group can be protected by esterification. Theesterification can be performed with R—OH or the like. A method known bythose skilled in the art can be applied as a specific condition of theesterification and the like. For example, the end can be protected andmodified by bonding polylactic acid to a raw material filler in areactor and then reacting an acid anhydride, diisocyanate or the likewithout isolating, or by isolating and then reacting diisocyanate or thelike in a kneader and a bi-axial extruder.

The above-described R is not especially limited as long as it is anormal organic group. Example thereof can include an alkyl group having1 to 12 carbon atoms such as methyl, ethyl, propyl, isopropyl, n-butyl,iso-butyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl,n-nonyl, n-decyl, n-undecyl and n-dodecyl; a substituted alkyl grouphaving 1 to 12 carbon atoms such as trifluoromethyl; an alkylene grouphaving 2 to 12 carbon atoms such as ethylene; a cycloalkyl group having3 to 10 carbon atoms such as cyclohexyl; and an aryl group such asphenyl.

Specific example of a reagent for the above-described protectionincludes acetic anhydride, acetic acid, acetic acid chloride, propionicanhydride, propionic acid, butyric anhydride, butyric acid, succinicanhydride, succinic acid, phthalic anhydride, phthalic acid, adipicacid, camphonic acid, cyclohexane diacetic acid, cyclopentane diaceticacid, adamantane dicarboxylic acid, norbornane dicarboxylic anhydride,norbornane dicarboxylic acid, norbornene dicarboxylic acid anhydride,norbornene carboxylic acid, 2,6-naphthalene dicarboxylic acid,1,4-naphthalene dicarboxylic acid, 1,5-naphthalene dicarboxylic acid,trifluoroacetic anhydride, trifluoroacetic acid, pentafluoropropionicanhydride, heptafluorobutylic anhydride, heptafluorobutyric acid,benzoic anhydride, benzoic acid, trifluoromethanesulfonic anhydride,trifluoromethanesulfonic acid, ethylisocyanate, propylisocyanate,sec-butylisocyanate, tert-butylisocyanate, pentylisocyanate,hexylisocyanate, heptylisocyanate, octylisocyanate,cyclohexylisocyanate, isophoronediisocyanate, phenylisocyanate,toluenediisocyanate, toluene-2,4-diisocyanate, toluene-2,6-diisocyanate,1,3-phenylenediisocyanate, 1,3-bis(isocyanatemethyl)benzene,1,3-bis(isocyanate-1-methylethyl)benzene,4,4′-methylenebis(phenyl)socyanate), 1,4-phenylenediisocyanate,1-chloromethyl-2,4-diisocyanatebenzene,4,4′-methylenebis(2,6-diphenylisocyanate),4,4′-oxybis(phenyl)socyanate), 1,4-diisocyanatebutane,1,6-diisocyanatehexane, 1,8-diisocyanateoctane,1,12-diisocyanatedodecane, 1,5-diisocyanate-2-methylpentane,trimethyl-1,6-diisocyanatehexane, 1,3-bis(isocyanatemethyl)cyclohexane,trans-1,4-cyclohexylenediisocyanate,4,4′-methylenebis(cyclohexylisocyanate), isophoronediisocyanate, RIKACID(registered trademark) TH, RIKACID HT-1A, RIKACID HH, RIKACID MH-700,RIKACID MT-500TZ, and RIKACID HNA-100 manufactured by New Japan ChemicalCo., Ltd., and these mixtures.

In case of using anhydride of divalent acid such as phthalic anhydrideas a reagent for protection, it is considered that the reagent reactswith two terminal hydroxy groups of polylactic acid to bond twopolylactic acids. However, it is also possible that the anhydride reactswith only one terminal hydroxyl group of the polylactic acid and acarboxyl group originated from the anhydride remains.

A method of modifying the raw material filler with the above-describedpolylactic acid (A) is not especially limited. However, for example, amethod of performing dehydration-polymerization of lactic acid and/or aring-opening polymerization of lactide in the presence of the rawmaterial filler is exemplified. Moreover, a method described in Japanesepublication of patent application Nos. Hei 9-143253 and Heil-206851 canbe used in these dehydrating polymerization and ring-openingpolymerization methods.

More specifically, the functional filler of the present invention can beproduced with a method including the steps of mixing lactic acidsolution and/or lactide solution or lactic acid melt and/or lactide meltwith the raw material filler; and polymerizing the lactic acid and/orlactide to modify the surface or end of the raw material filler withpolylactic acid. Such method of producing the functional filler is alsoone of the present invention. Hereinafter, the condition and the like ofeach step will be described.

First, a solution of lactic acid and/or lactide or a melt of lactic acidand/or lactide is mixed with the raw material filler. Toluene can bepreferably used as a solvent of the solution. In the next polymerizationstep, the reaction is carried out while water generated by thepolymerization is removed. In such a reaction, benzene or toluene can begenerally used. However, since the boiling point of benzene isrelatively low and there is a fear that the reaction does not proceedwell, toluene is preferably used. Further, since the melting point oflactic acid is about 53° C. and the melting point of lactide is 124° C.,the melt can be easily produced by bringing the temperature to themelting points or more. The mixing method is not especially limited, andthe raw material filler may be added and mixed to the above-describedsolution or melt, or the raw material filler may be mixed with lacticacid or the like and then the solvent may be added, or lactic acid orthe like may be melted.

In case that the raw material filler does not have a functional groupcapable of being bonded to lactic acid or polylactic acid on the surfaceor end, the functional group may be introduced using a known method.Specifically, there is a method of mixing alkoxysilane in which at leastone alkoxyl group is substituted with a functional group such as anaminoalkyl group and an epoxyalkyl group with the raw material filler,and modifying the surface of the raw material filler while alkoxysilaneis polymerized.

The ratio of lactic acid or the like and the raw material filler may beadjusted appropriately depending on the amount of polylactic acid (A) tobe bonded to the raw material filler, that is the number and the eachmolecular weight of the polylactic acid (A) to be bonded, and whetherpolylactic acid which is not bonded to the raw material filler is madeto remain or not. Further, the ratio is adjusted depending on the typeof the raw material filler. For example, in case of divalent alcoholhaving only two functional groups capable of being bonded to polylacticacid, the amount of lactic acid and the like should be relatively less.On the other hand, in case of using a raw material filler capable ofbonding a lot of polylactic acid and the like on the surface such as asurface modified silica, the amount of lactic acid and the like may berelatively more. Further, though the concentration of the solution oflactic acid and the like is not especially limited, for example, theconcentration can be made to be about 40 to 80% by mass. In the stage ofthis step, a completed solution is not necessarily used, and asuspension in which a part of lactic acid and the like is not dissolved.

Next, the temperature of the mixed liquid obtained in the mixing step isincreased to promote the polymerization reaction. At the same time asthe polymerization of lactic acid, a polylactic acid is bonded to areactive group on the surface or end of the raw material filler. At thistime, a general polymerization catalyst may be added. However,considering the possibility of not performing the purification of thefunctional filler, it is preferable not to use a catalyst. Thepolymerization reaction proceeds by increasing the temperature to about100 to 250° C. Further, the polymerization can proceed even more byintroducing inert gas such as argon gas and nitrogen gas, or removingwater in the reaction system. The reaction time can be, but notespecially limited to, about 5 to 20 hours. Moreover, by adjusting thereaction temperature and the reaction time depending on the reactionsubstrate, the degree of polymerization of the polylactic acid can beadjusted.

Other than the above-described production method, polylactic acid to bebonded is synthesized separately, and then the polylactic acid can bebonded to the raw material filler. This method is effective for the caseof bonding a special polylactic acid such as a block copolymer. Beforepolylactic acid is bonded to the raw material filler, the terminalhydroxy group or the terminal carboxyl group of the polylactic acid maybe activated.

After completion of the reaction, the reaction mixture is dissolved intochloroform, dioxane or the like, and then the mixture may be refined byreprecipitating the functional filler with priority by gradually addingmethanol or ethanol which is a poor solvent of the polylactic acid andcollecting this precipitant. However, the mixture may be used as it isas the mixture with a non-bonded polylactic acid.

Further, after purification of the functional filler, an increase of themolecular weight may be attempted by performing further solid-phasepolymerization by heating under reduced pressure in a solid statedepending on necessity.

In the above-described production method, the functional fillercomposition containing polylactic acid which is not bonded to the rawmaterial slurry can be produced by using an excess amount of lactic acidand/or lactide to the raw material filler and not performing morepurification than necessary. Such a functional filler composition andsuch a production method are one embodiment of the present invention.

The functional filler composition of the present invention contains theabove-described functional filler and a non-bonded polylactic acidproduced during production of the functional filler. Since such resincomposition can be produced by omitting a purification step, thecomposition has an advantage in the aspect of cost.

In case of protecting a hydroxy group or a carboxyl group at the end ofpolylactic acid which modifies the surface or end of the raw materialfiller in the functional filler composition, at least one part of theend of the non-bonded polylactic acid is also assumed to be protectedthe same. Such a functional filler composition is included in the scopeof the present invention.

The functional filler composition of the present invention ischaracterized in including the above functional filler and polylacticacid as a matrix polymer, in which at least one part of the polylacticacid interacts with polylactic acid which modifies the surface or end ofthe functional filler. Since polylactic acid as a matrix polymer caninteract with polylactic acid which is bonded to the functional fillerin this resin composition, the functional filler cross-links multiplematrix polymers, and heat resistance, strength or the like of thecomposition material can be remarkably increased. Hereinafter,polylactic acid which is a matrix polymer is sometimes referred to as“polylactic acid (B)”.

At least a part of Polylactic acid (B) as a matrix polymer can interactwith polylactic acid (A) bonding to the functional filler. When at leastone part of polylactic acid (B) can interact with polylactic acid (A),multiple polylactic acids (B) is crosslinked by polylactic acid (A), andheat resistance or the like can be improved. For expecting even moreimprovement of the effect, polylactic acid (B) showing a stronginteraction with polylactic acid (A) is preferably used. For example, incase that polylactic acid (A) is poly-L-lactic acid, poly-D-lactic acidis preferably used as polylactic acid (B). Further, a mixture ofpolylactic acid may be used as polylactic acid (B), and in this case, afunctional filler may be used in which the surface or end is modifiedwith the mixture of polylactic acid.

Poly-L-lactic acid and poly-D-lactic acid can be obtained by directlycondensating L-lactic acid or D-lactic acid obtained with a fermentationmethod from a plant raw material, for example, as shown in Japanesepublication of patent application No Hei 9-143253. Further, as shown inJapanese publication of patent application No. Hei 7-206851, a similarpoly-L-lactic acid and poly-D-lactic acid can be obtained also byperforming ring-opening polymerization on a cyclic dimer, i.e. D-lactideor L-lactide, obtained by thermally decomposing a low molecularcondensation product of lactic acid, i.e. lactic acid oligomer.

For the preferred molecular weight of the above-described polylacticacid (B) used in the present invention, the best value is determined bythe object, usage, necessary performance or molding method. The numberaverage molecular weight (Mn) in terms of polystyrene is 50,000 or more,preferably 100,000 or more, and more preferably 120,000 to 500,000. Thenumber average molecular weight of the present invention is measuredwith GPC (gel permeation chromatography) with an1,1,1,3,3,3-hexafluoro-2-isopropanol solvent. Moreover, the weightaverage molecular weight of polylactic acid is normally 1.1 to 5×Mn, andpreferably 1.1 to 3×Mn. However, in special uses such as the use offoaming and inflation film, polylactic acid having molecular weightother than this range can be also sufficiently used.

The non-bonded polylactic acid produced during production of thefunctional filler may be blended in the resin composition of the presentinvention. This polylactic acid may be added other than the functionalfiller and the matrix polymer of the present invention, however, thepolylactic acid is included in the above-described functional fillercomposition of the present invention. Therefore, in case that thefunctional filler and the matrix polymer of the present invention aremixed, the polylactic acid is naturally blended. Hereinafter, thenon-bonded polylactic acid produced at the production of the functionalfiller is sometimes referred to as “polylactic acid (C)”.

In case that at least one part of polylactic acid (C) interacts withpolylactic acid (B), for example, in case that the polylactic acid (A)and polylactic acid (C) are poly-L-lactic acid and the polylactic acid(B) is poly-D-lactic acid, or in case that polylactic acid (A) andpolylactic acid (C) are poly-D-lactic acid and polylactic acid (B) ispoly-L-lactic acid, at least one part of polylactic acid (A) and/orpolylactic acid (C) and the above-described polylactic acid (B) can forma stereo complex.

Whether there is a stereo complex of the functional filler of thepresent invention and polylactic acid (B) as a matrix polymer orpolylactic acid (B) and polylactic acid (C) can be determined easily inthat a new melting point (Tm2) is shown at a higher temperature than amelting point (Tm1) of poly-L-lactic acid or poly-D-lactic acid. Heat ofdiffusion (ΔHm2) at the melting point (Tm2) is proportional to theamount of poly-D-lactic acid in poly-L-lactic acid or the amount ofpoly-L-lactic acid in poly-D-lactic acid. From this, quantification ofthe stereo complex amount in poly-L-lactic acid or the stereo complexamount in poly-D-lactic acid becomes possible.

The above-described functional filler and/or the functional fillercomposition in the resin composition of the present invention ispreferably 0.01 part by mass or more per 100 parts by mass of matrixpolymer. When the amount is 0.01 part by mass or more, the physicalproperties improving effect by the addition of the functional filler canbe secured sufficiently. It is more preferably 0.5 part by mass or more,and further preferably 1 part by mass or more. On the other hand, whenthe functional filler is added excessively, there is a case that thestrength of the resin composition rather decreases. Therefore, the addedamount of the functional filler is preferably 50 parts by mass or lessand more preferably 30 parts by mass or less per 100 parts by mass ofmatrix polymer.

The heat resistance of the resin composition of the present invention ispreferably the heat resistance in which the deformation amount is lessthan 10 mm in a heat sag test of 110° C. or more. Here, theabove-described heat sag test is performed by heating for 1 hour at atemperature of 110° C. or more according to JIS K7195. A test piece isproduced by cutting out the resin composition which is molded with a hotpress into a prescribed size with a hot cutter. Here, good heatresistance refers to the case that the deformation amount is 10 mm orless. More preferred heat resistance refers to a small deformationamount in a heat sag test with higher temperature. When the deformationamount at 110° C. or more is 10 mm or more, heat resistance isinsufficient and the composition becomes inappropriate depending on theuse. The more preferred heat resistance is that the deformation amountis less than 10 mm in a heat sag test at 120° C. or more, and furtherpreferably less than 10 mm at 130° C. or more.

The resin composition of the present invention preferably has hightransparency. The light transmittance at 550 nm when the resincomposition of the present invention is molded into a sheet sample of0.2 mm thickness is preferably 70% or more, and more preferably 75% ormore.

Since the homogenously dispersed functional filler functions as anucleating agent in the resin composition of the present invention, thecrystallization speed of the resin composition becomes fast, and moldingspeed, stretching temperature and stretching ratio can be improved.Therefore, physical properties and moldability of the obtained moldedproduct can be improved, and thus applications can be expanded. Further,since a spherical-shaped crystal size is small even in case ofcrystallization, the transparency is maintained, and brittleness of themolded body is improved without distraction at the interface or thespherical-shaped crystal. In the resin composition of the presentinvention, the degree of crystallization is preferably 25% or more. Whenthe degree of crystallization is less than 25%, heat resistance andmechanical strength of the molded body is insufficient depending on theuse, since heat resistance and the modulus of elasticity are low. Morepreferably the degree is 30% or more, and further preferably 35 to 80%.The degree of crystallization of the resin composition can be measuredusing a differential scanning calorimeter such as Rigaku DSC8230manufactured by Rigaku Cooperation.

The resin composition of the present invention can be made into a heatresistant flame-retardant material by kneading various flame-retardantagents. Example of the flame retardant agents includes a halogenantimony-based flame-retardant agent, an environment-responsive typeflame-retardant agent or the like. The environment-responsive typeflame-retardant agent is mainly used.

Example of the environment-responsive type flame-retardant agentincludes a silicone-based flame-retardant agent, a phosphorus-basedflame-retardant agent, a metal hydroxide-based flame-retardant agent, anitrogen-based flame-retardant agent or the like.

Example of the silicone-based flame-retardant agent includes SZ6018which is phenylsilicone manufactured by Dow Corning Cooperation,DC4-7081 which is methacryl group-containing polymethylsiloxanemanufactured by Dow Corning Cooperation, MB50-315 which ispolycarbonate+polydimethylsiloxane manufactured by Dow CorningCooperation, X40-9805 which is methylphenyl-based silicone manufacturedby Shin-Etsu Chemical Co., Ltd., XC99-B5664 which is phenylsiliconemanufactured by GE Toshiba Silicone Co., Ltd. or the like.

Example of the phosphorus-based flame-retardant agent includes anAP-based flame-retardant agent, an OP-based flame-retardant agent, aTPP-based flame-retardant sold from Clarient, Inc.; aromatic condensatedphosphoric acid ester such as PX-200 manufactured by Daihachi ChemicalIndustry Co., Ltd.; ammonium polyphosphate such as Fire Cut FCP730manufactured by Suzuhiro Chemical Co., Ltd.; triphenylphosphate soldfrom Daihachi Chemical Industry Co., Ltd. or the like.

Example of the metal hydroxide-based flame-retardant agent includesBF01ST (average particle size: 1 μm, KISMER 5A) which is aluminumhydroxide manufactured by Nippon Light Metal Co., Ltd. or the like.

Example of the nitrogen-based flame-retardant agent includes Stabaxol Iwhich is a mixture having bis(dipropylphenyl)carbodiimide as a maincomponent manufactured by Rhein Chemie; Stabaxol P which is a mixture ofaromatic monocarbodiimide (95%) and silica (5%) manufactured by RheinChemie; melamine compounds such as melamine cyanurate, dimelaminephosphate and melamine borate such as MC-440 manufactured by NissanChemical Industries, Ltd.; guanidine compound such as guanidinesulfamate, guanidine phosphate and guanylurea phosphate, such as Apinoneseries manufactured by Sanwa Chemical Co., Ltd. and Melar seriesmanufactured by Monsanto Company or the like.

In the resin composition of the present invention, variouscharacteristics such as mechanical characteristics and a gas barriercharacteristic can be improved further by kneading the raw materialfiller of the functional filler of the present invention.

By adding the functional filler of the present invention, thedispersibility or compatibility of the matrix polymer with otherpolymers such as polycarbonate, polyethyleneterephthalate andpolypropylene, additives such as dye or the like can be improved.

The production method of the resin composition of the present inventionis not especially limited. However, the resin composition can beproduced with a method including the steps of mixing lactic acid and/orlactide solution or lactic acid melt and/or lactide melt with the rawmaterial filler; polymerizing the lactic acid and/or latcide to modifythe surface or end of the raw material filler with polylactic acid toobtain the functional filler; and mixing the functional filler with thepolylactic acid as a matrix polymer at least partly interacting withpolylactic acid modifying the surface or end of the functional filler.Such a production method of the resin composition is also one embodimentof the present invention.

In the above-described production method, the functional filler and thematrix polymer may be mixed in a solvent. However, since a drying stepis necessary and the solvent itself is harmful to a living body, themelt mixing is preferably performed at a temperature of the meltingpoint of at least one of the components or more.

In the production method of the resin composition of the presentinvention, a normal method for removing a solvent can be adapted as amethod of removing the solvent used in the production of the functionalfiller. Specifically, a method of removing by heating under atmosphereor reduced pressure during mixing in a laboratory plastomill or abiaxial extruder or the like is preferably used.

A molded body including the resin composition of the present inventionis also one embodiment of the present invention. Example of such amolded body includes a molded body by injection molding method, a moldedbody by extrusion molding method, a molded body by inflation moldingmethod, a molded body by blow molding method, a molded body by transfermolding method, a molded body by pressure compressed molding method, afiber structured product and a molded body by molding method used in amethod of a normal plastic molding. Though melt characteristics andsolidifying and crystallization characteristics are important elementswhen the resin composition is applied to each of these molding methods,optimization can be performed easily to any of the molding methods ofthe present invention.

EXAMPLES

Hereinafter, the present invention will be described in more detail byshowing Examples. However, the present invention is not limited to theseExamples.

Production Example 1 Production of Functional Filler Composition inWhich the Surface of the Filler is Treated with Low Molecular WeightPolylactic Acid

[1] Production of Surface-Aminated Silica, and Production ofD-Form-Modified Functional Filler Composition Using the Silica

(1) Production of Surface-Aminated Silica

SYLOSPHERE (registered trademark) C-1504 (average particle size: 4 μm,56 g) which was a spherical silica manufactured by Fuji Silysia ChemicalLtd., was dispersed into ethanol (1.5 l) in which water (75 ml) wasadded. Then, 3-aminopropyltriethoxysilane (15 g) was added, and theresulting mixture was stirred at room temperature for 24 hours.

The silica particles were filtered under reduced pressure, cleaned withethanol, and then dried at 100° C. to obtain surface-aminated silica (62g). The obtained surface-aminated silica was almost transparent. Thisshows that the surface of the spherical silica is aminated, and mutualcoagulation of silica is eliminated.

(2) Production of D-Form-Modified Functional Filler Composition <Sample1>

The surface-aminated silica (5 g) obtained in (1) was dispersed intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 50 g), andthe resulting solution was stirred overnight at 140° C. under argonbubbling to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 30 g of yellowish brown and almost transparentD-form-modified functional filler composition.

The fact that the obtained D-form-modified functional filler compositionis almost transparent shows that coagulation of silica particles iseliminated by bonding poly-D-lactic acid on the surface of the silicaparticles.

(3) Production of D-Form-Modified Functional Filler Composition <Sample2>

The surface-aminated silica (10 g) obtained in (1) was dispersed intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 50 g), andthe resulting solution was stirred overnight at 140° C. under argonbubbling to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 34 g of yellowish brown and almost transparentD-form-modified functional filler composition. The fact that theobtained D-form-modified functional filler composition is almosttransparent shows that coagulation of silica particles is eliminated bybonding poly-D-lactic acid on the surface of the silica particles.

(4) Production of D-Form-Modified Functional Filler Composition <Sample3>

The surface-aminated silica (40 g) obtained in (1) and D-lactic acid(manufactured by PURAC, 90% by mass solution, 80 g) was dissolved anddispersed into toluene (120 ml), and water was removed under refluxusing a water measuring tube under an argon atmosphere to performdehydration polymerization to obtain yellowish brown and almosttransparent D-form-modified functional filler composition. The fact thatthe obtained D-form-modified functional filler composition is almosttransparent shows that coagulation of silica particles is eliminated bybonding poly-D-lactic acid on the surface of the silica particles.

The toluene solution of this D-form-modified functional fillercomposition was used in the next experiment as it was.

[2] Production of D-Form-Modified Functional Filler Composition <Sample4>

A methanol suspension (16.5 g) of silica sol manufactured by NissanChemical Co., Ltd., was dispersed into D-lactic acid (manufactured byPURAC, 90% by mass solution, 50 g), and the resulting solution wasstirred overnight at 140° C. under argon bubbling to perform dehydrationpolymerization.

After completion of the reaction, about 27 g of colorless andtransparent D-form-modified functional filler composition was obtainedby cooling and solidifying and scraping out the solid with a spatula.

[3] Production of Surface-Epoxidated Silica, and Production of aD-Form-Modified Functional Filler Composition Using the Silica

(1) Production Method of Surface-Epoxidated Silica

SYLOSPHERE C-1504 (average particle size: 4 μm, 52 g) which was aspherical silica manufactured by Fuji Silysia Chemical Ltd., wasdispersed into ethanol (1.5 l) in which water (75 ml) was added, andthen pH was adjusted to about 4 by adding acetic acid. Next,3-glycideoxypropyltrimethoxysillane (16 g) was added, and the resultingmixture was stirred at room temperature for 24 hours.

The silica particles were filtered under reduced pressure, cleaned withethanol, and then dried at 100° C. to obtain surface-epoxidated silica(54 g).

(2) Production of D-Form-Modified Functional Filler Composition <Sample5>

The surface-epoxidated silica (10 g) obtained in (1) was dispersed intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 50 g), andthe resulting solution was stirred overnight at 140° C. under argonbubbling to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 30 g of colorless and almost transparent D-form-modifiedfunctional filler composition. The fact that the obtainedD-form-modified functional filler composition is almost transparentshows that silica particles are dispersed into poly-D-lactic acid in astate of almost primary particles.

[4] Production of D-Form-Modified Functional Filler Composition <Sample6>

KUNIPIA P (10 g) which was montmorillonite manufactured by KunimineIndustries Co., Ltd., was dispersed into D-lactic acid (manufactured byPURAC, 90% by mass solution, 100 g), and the resulting solution wasstirred overnight at 140° C. under argon bubbling to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 65 g of grey green D-form-modified functional fillercomposition.

[5] Production of D-Form-Modified Functional Filler Composition <Sample7>

AEROSIL SILICA 50 (5 g) which was a silica particle manufactured byNippon Aerosil Co., Ltd., and D-lactic acid (manufactured by PURAC, 90%by mass solution, 50 g) were mixed. In the beginning of the reaction,the mixture became solid by absorption of D-lactic acid by Aerosil andwas not homogenous. However, when the mixture was reacted at 140° C.under argon bubbling, the mixture gradually became a homogenoussolution. Further, dehydration polymerization was performed understirring overnight.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 32 g of colorless and almost transparent D-form-modifiedfunctional filler composition. The fact that the obtainedD-form-modified functional filler composition is almost transparentshows that coagulation of silica particles is eliminated by bondingpoly-D-lactic acid on the surface of the silica particles.

[6] Production of L-Form-Modified Functional Filler Composition <Sample8>

AEROSIL SILICA 50 (5 g) which was a silica particle manufactured byNippon Aerosil Co., Ltd., and L-lactic acid (manufactured by NacalaiTesque, 90% by mass solution, 50 g) were mixed. In the beginning of thereaction, the mixture became solid by the absorption of D-lactic acid byAEROSIL and was not homogenous. However, when the mixture was reacted at140° C. under argon bubbling, the mixture gradually became a homogenoussolution. Further, dehydration polymerization was performed understirring overnight.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 32 g of colorless and almost transparent L-form-modifiedfunctional filler composition. The fact that the obtainedL-form-modified functional filler composition is almost transparentshows that silica particles are dispersed into poly-L-lactic acid in astate of almost primary particles.

[7] Production of D-Form-Modified Functional Filler Composition <Sample9>

Fiber hydroxyapatite (3.7 g) manufactured by Ube Material Industries,Ltd., was dispersed into D-lactic acid (manufactured by PURAC, 90% bymass solution, 37 g), and the resulting solution was stirred overnightat 140° C. under argon bubbling to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 27 g of white D-form-modified functional fillercomposition.

[8] Production of D-Form-Modified Functional Filler Composition <Sample10>

A pulp sheet (9 g) was broke up into fibers with a mixer and water waspartially remove to obtain 40 g of lump. A mixture of the lump, D-lacticacid (manufactured by PURAC, 90% by mass solution, 50 g) and water (50g) was stirred overnight at 140° C. under argon bubbling to performdehydration polymerization.

After completion of the reaction, the mixture was cooled and solidified,and about 33 g of yellowish brown D-form-modified functional fillercomposition was obtained by scraping with a spatula.

[9] Production of D-Form-Modified Functional Filler Composition <Sample11>

Pentaerythritol (2.5 g) was dispersed into D-lactic acid (manufacturedby PURAC, 90% by mass solution, 73 g), and the resulting mixture wasstirred for 2 days at 140° C. under argon bubbling to performdehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 69 g of colorless and transparent D-form-modifiedfunctional filler composition.

[10] Production of D-Form-Modified Functional Filler Composition <Sample12>

Pentaerythritol (5 g) was dissolved into D-lactic acid (manufactured byPURAC, 90% by mass solution, 73 g), and the resulting solution wasstirred for 2 days at 140° C. under argon bubbling to performdehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 66 g of colorless and transparent D-form-modifiedfunctional filler composition.

[11] Production of D-Form-Modified Functional Filler Composition <Sample13>

Trimesic acid (2.5 g) was dispersed into D-lactic acid (manufactured byPURAC, 90% by mass solution, 71 g), and the resulting mixture wasstirred overnight at 140° C. under argon bubbling to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 70 g of white D-form-modified functional fillercomposition.

[12] Production of D-Form-Modified Functional Filler Composition <Sample14>

Dipentaerythritol (5 g) was dissolved into D-lactic acid (manufacturedby PURAC, 90% by mass solution, 108 g), and the resulting solution wasstirred overnight at 140° C. under argon bubbling to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 73 g of colorless and transparent D-form-modifiedfunctional filler composition.

[13] Production of D-Form-Modified Functional Filler Composition <Sample15>

AEROSIL SILICA 300 (30 g) which was a silica nano-particle manufacturedby Nippon Aerosil Co., Ltd., was mixed with D-lactic acid (manufacturedby PURAC, 90% by mass solution, 300 g). In the beginning of thereaction, the mixture became solid by absorption of D-lactic acid byAerosil and was not homogenous. However, when the mixture was reacted at140° C. under argon bubbling, the mixture gradually became a homogenoussolution. Further, dehydration polymerization was performed understirring overnight.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 220 g of colorless and almost transparentD-form-modified functional filler composition.

[14] Production of D-Form-Modified Functional Filler Composition <Sample16>

PILATEX-LB (a 38.9% by mass solution, 100 g) which was latexmanufactured by Nippon A and L Co., Ltd., was mixed with D-lactic acid(manufactured by PURAC, 90% by mass solution, 300 g), and the resultingmixture was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization. At the polymerization, generation of foam was intenseand a half or more of the polymerization product flowed out).

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 70 g of brown and semi-transparent D-form-modifiedfunctional filler composition.

[15] Production of D-Form-Modified Functional Filler Composition <Sample17>

Polytetrahydrofran (molecular weight 650, 23.1 g) was dissolved intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 215 g), andthe resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 145 g of colorless and transparent D-form-modifiedfunctional filler composition.

[16] Production of D-form-modified functional filler composition <Sample18>

Polytetrahydrof ran (molecular weight: 250, 17.8 g) was dissolved intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 427 g), andthe resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 325 g of colorless and transparent D-form-modifiedfunctional filler composition.

[17] Production of D-Form-Modified Functional Filler Composition <Sample19>

Myo-inositol (10.0 g) was dissolved into D-lactic acid (manufactured byPURAC, 90% by mass solution, 1000 g), and the resulting solution wasstirred overnight at 130° C. under argon bubbling and further stirredovernight at 160° C. to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 750 g of almost colorless and transparentD-form-modified functional filler composition.

[18] Production of D-Form-Modified Functional Filler Composition <Sample20>

Polyethylene glycol (molecular weight: 600, 90 g) was dissolved intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 900 g), andthe resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 790 g of colorless and transparent D-form-modifiedfunctional filler composition.

[19] Production of D-Form-Modified Functional Filler Composition <Sample21>

Tetraethoxysilane (50.0 g) was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 450 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 250 g of colorless and transparent D-form-modifiedfunctional filler composition.

[20] Production of D-Form-Modified Functional Filler Composition <Sample22>

Methyltriethoxysilane (37.5 g) was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 150 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 95 g of white D-form-modified functional fillercomposition.

[21] Production of D-Form-Modified Functional Filler Composition <Sample23>

SILA-ACE S330 (61 g) which was 3-aminopropyltrialkoxysilane manufacturedby Chisso Cooperation was dissolved into D-lactic acid (manufactured byPURAC, 90% by mass solution, 830 g), and the resulting solution wasstirred overnight at 130° C. under argon bubbling and further stirredovernight at 160° C. to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 600 g of yellow and transparent D-form-modifiedfunctional filler composition.

[22] Production of D-Form-Modified Functional Filler Composition <Sample24>

SILA-ACE S510 (35 g) which was 3-glycidoxypropyltrialkoxysilanemanufactured by Chisso Cooperation was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 900 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 640 g of colorless and transparent D-form-modifiedfunctional filler composition.

[23] Production of D-Form-Modified Functional Filler Composition <Sample25>

Melamine (15 g) was dissolved into D-lactic acid (manufactured by PURAC,90% by mass solution, 1071 g), and the resulting solution was stirredovernight at 130° C. under argon bubbling and further stirred overnightat 160° C. to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 750 g of yellow and nontransparent D-form-modifiedfunctional filler composition.

[24] Production of D-Form-Modified Functional Filler Composition <Sample26>

SILAPLANE FMDA 11 (30 g) which was both terminal-hydroxylatedpolydimethyl(phenyl)siloxane manufactured by Chisso Cooperation wasdispersed into D-lactic acid (manufactured by PURAC, 90% by masssolution, 300 g), and the resulting mixture was stirred overnight at130° C. under argon bubbling and further stirred overnight at 160° C. toperform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 220 g of colorless and transparent D-form-modifiedfunctional filler composition.

[25] Production of D-Form-Modified Functional Filler Composition <Sample27>

SILAPLANE FM3311 (30 g) which was both terminal-aminatedpolydimethyl(phenyl)siloxane manufactured by Chisso Cooperation wasdispersed into D-lactic acid (manufactured by PURAC, 90% by masssolution, 300 g), and the resulting mixture was stirred overnight at130° C. under argon bubbling and further stirred overnight at 160° C. toperform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 230 g of yellow and transparent D-form-modifiedfunctional filler composition.

[26] Production of D-Form-Modified Functional Filler Composition <Sample28>

1,4-Phenylenediamine (5.6 g) was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 515 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 350 g of yellow and transparent D-form-modifiedfunctional filler composition.

[27] Production of D-Form-Modified Functional Filler Composition <Sample29>

Hexamethylenediamine (3.4 g) was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 302 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 190 g of yellow and transparent D-form-modifiedfunctional filler composition.

[28] Production of L-Form-Modified Functional Filler Composition <Sample30>

1,4-Phenylenediamine (8.3 g) was dissolved into L-lactic acid(manufactured by Musashino Chemical Laboratory, Ltd., 90% by masssolution, 773 g), and the resulting solution was stirred overnight at130° C. under argon bubbling and further stirred overnight at 160° C. toperform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 590 g of yellow and transparent L-form-modifiedfunctional filler composition.

[29] Production of L-Form-Modified Functional Filler Composition <Sample31>

Hexamethylenediamine (6.8 g) was dissolved into L-lactic acid(manufactured by Musashino Chemical Laboratory, Ltd., 90% by masssolution, 604 g), and the resulting solution was stirred overnight at130° C. under argon bubbling and further stirred overnight at 160° C. toperform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 430 g of yellow and transparent L-form-modifiedfunctional filler composition.

[30] Production of D-Form-Modified Functional Filler Composition <Sample32>

4,4′-Biphenol (9.3 g) was dissolved into D-lactic acid (manufactured byPURAC, 90% by mass solution, 500 g), and the resulting solution wasstirred overnight at 130° C. under argon bubbling and further stirredovernight at 160° C. to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 340 g of colorless and transparent D-form-modifiedfunctional filler composition.

[31] Production of D-Form-Modified Functional Filler Composition <Sample33>

Zirconium tetrapropoxide (70%, 1-propanol solution, 50 g) was dispersesdinto D-lactic acid (manufactured by PURAC, 90% by mass solution, 250 g),and the resulting mixture was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and was cooled to obtain about170 g of white solid D-form-modified functional filler composition.

[32] Production of D-Form-Modified Functional Filler Composition <Sample34>

1,3,5-Tris(2-hydroxyethyl)cyanuric acid (20 g) was dissolved intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 1150 g), andthe resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 800 g of colorless and transparent D-form-modifiedfunctional filler composition.

[33] Production of D-Form-Modified Functional Filler Composition <Sample35>

N,N′-Bis(2-hydroxyethyl)oxamide (21.1 g) was dissolved into D-lacticacid (manufactured by PURAC, 90% by mass solution, 1200 g), and theresulting solution was stirred overnight at 130° C. under argon bubblingand further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 845 g of yellow and transparent D-form-modifiedfunctional filler composition.

[34] Production of D-Form-Modified Functional Filler Composition <Sample36>

Bisphenol (22.8 g) was dissolved into D-lactic acid (manufactured byPURAC, 90% by mass solution, 1200 g), and the resulting solution wasstirred overnight at 130° C. under argon bubbling and further stirredovernight at 160° C. to perform dehydration polymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 837 g of yellow and transparent D-form-modifiedfunctional filler composition.

[35] Production of D-Form-Modified Functional Filler Composition <Sample37>

UC-CARB 100 (molecular weight: 1000, 98 g) which was polycarbonatediolmanufactured by Ube Industries, Ltd., was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 980 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 755 g of colorless and transparent D-form-modifiedfunctional filler composition.

[36] Production of D-Form-Modified Functional Filler Composition <Sample38>

Polycarbonatediol UH-200 (molecular weight: 1000, 150 g) which waspolycarbonatediol manufactured by Ube Industries, Ltd., was dissolvedinto D-lactic acid (manufactured by PURAC, 90% by mass solution, 750 g),and the resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 645 g of colorless and transparent D-form-modifiedfunctional filler composition.

[37] Production of D-Form-Modified Functional Filler Composition <Sample39>

Pentaerythritol (8.19 g) was dissolved into D-lactic acid (manufacturedby PURAC, 90% by mass solution, 1200 g), and the resulting solution wasstirred overnight at 130° C. under argon bubbling and further stirredovernight at 160° C. to perform dehydration polymerization. Theterminal-hydroxy groups were acetylated by decreasing the reactiontemperature to about 110° C., adding acetic anhydride (25 g), andfurther stirring overnight at 160° C.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 805 g of colorless and transparent D-form-modifiedfunctional filler composition.

[38] Production of D-Form-Modified Functional Filler Composition <Sample40>

UC-CARB 100 (molecular weight: 1000, 200 g) which was polycarbonatediolmanufactured by Ube Industries, Ltd., was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 800 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization. The terminal-hydroxy groups were acetylated bydecreasing the reaction temperature to about 110° C., adding aceticanhydride (41 g), and further stirring overnight at 160° C.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 790 g of colorless and transparent D-form-modifiedfunctional filler composition.

[39] Production of D-Form-Modified Functional Filler Composition <Sample41>

Poltethylene glycol (molecular weight: 600, 100 g) was dissolved intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 1000 g), andthe resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization. The terminal-hydroxy groups were acetylated bydecreasing the reaction temperature to about 110° C., adding aceticanhydride (35 g), and further stirring overnight at 160° C.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 850 g of colorless and transparent D-form-modifiedfunctional filler composition.

[40] Production of D-Form-Modified Functional Filler Composition <Sample42>

Polytetrahydrofran (molecular weight 2000, 300 g) was dissolved intoD-lactic acid (manufactured by PURAC, 90% by mass solution, 900 g), andthe resulting solution was stirred overnight at 130° C. under argonbubbling and further stirred overnight at 160° C. to perform dehydrationpolymerization. The terminal-hydroxy groups were acetylated bydecreasing the reaction temperature to about 110° C., adding aceticanhydride (31 g), and further stirring overnight at 160° C.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 780 g of colorless and transparent D-form-modifiedfunctional filler composition.

[41] Production of D-Form-Modified Functional Filler Composition <Sample43>

UC-CARB 100 (molecular weight: 1000, 200 g) which was polycarbonatediolmanufactured by Ube Industries, Ltd., was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 800 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization. After the reaction temperature was decreased to about110° C., RIKACIDHNA-100 (alicyclic acid anhydride manufactured by NewJapan Chemical Co., Ltd., 28.8 g) was added and the mixture was stirredfurther overnight at 160° C.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 710 g of colorless and transparent D-form-modifiedfunctional filler composition.

[42] Production of D-Form-Modified Functional Filler Composition <Sample44>

UC-CARB100 (molecular weight: 1000, 200 g) which was polycarbonatediolmanufactured by Ube Industries, Ltd., was dissolved into D-lactic acid(manufactured by PURAC, 90% by mass solution, 800 g), and the resultingsolution was stirred overnight at 130° C. under argon bubbling andfurther stirred overnight at 160° C. to perform dehydrationpolymerization. After the reaction temperature was decreased to about110° C., isophoronediisocyanate 35.5 g) was added and the mixture wasstirred further overnight at 170° C.

After completion of the reaction, a fluid polymer was transferred to aTeflon (registered trademark) container, and then cooled and solidifiedto obtain about 690 g of colorless and transparent D-form-modifiedfunctional filler composition.

The D-form-modified functional filler compositions and theL-form-modified functional filler compositions obtained in ProductionExample 1 are summarized and shown in Table 1.

TABLE 1 Sample Raw material Raw material number filler filler sizeFiller property Notes 1 Amino silica 3 μm Colorless and transparent 2Amino silica 3 μm Colorless and transparent 3 Amino silica 3 μmYellowish brown and transparent 4 Silica dispersed 10-20 μm Colorlessand in methanol transparent 5 Epoxysilica 3 μm Colorless and transparent6 Kunipia P A few nm Grey-green and non- transparent 7 Aerosil silica 50A few Colorless and dozens nm transparent 8 Aerosil silica 50 A fewColorless and L-lactic acid dozens nm transparent was used. 9Hydroxyapatite A few μm White and non-transparent 10 Pulp A few μmYellowish brown and non-transparent 11 Pentaerythritol Colorless andtransparent 12 Pentaerythritol Colorless and transparent 13 Trimesicacid White and non-transparent 14 Dipentaerythritol Colorless andtransparent 15 Aerosil silica 300 Colorless and transparent 16Pilatex-LB Brown and semi-transparent 17 Polytetrahydrofran Colorlessand 650 transparent 18 Polytetrahydrofran Colorless and 250 transparent19 myo-Inositol Colorless and transparent 20 PEG600 Colorless andtransparent 21 Tetraethoxysilane Colorless and transparent 22Methyltriethoxy- white and silane semi-transparent 23 Sila-ace S330Yellow and transparent 24 Sila-ace S510 Colorless and transparent 25Melamine Yellow and non-transparent 26 Silaplane FMDA11 Colorless andtransparent 27 Silaplane FM3311 Yellow and transparent 28Phenylenediamine Yellow and transparent 29 Hexamethylene- Yellow anddiamine transparent 30 Phenylenediamine Yellow and L-lactic acidtransparent was used. 31 Hexamethylene- Yellow and L-lactic acid diaminetransparent was used. 32 4,4′-biphenol Colorless and transparent 33Zirconium White and tetrapropoxide non-transparent 341,3,5-Tris(2-hydroxy- Colorless and ethyl)cyanuric acid transparent 35N,N′-bis(hydroxy- Yellow and ethyl)oxide transparent 36 Bisphenol Yellowand transparent 37 Polycarbonatediol Colorless and transparent 38Polycarbonatediol Colorless and transparent 39 Pentaerythritol Yellowand Terminal modified transparent 40 Polycarbonatediol Yellow andTerminal modified transparent 41 Polyethylene glycol Colorless andTerminal modified transparent 42 Polytetrahydrofran Colorless andTerminal modified transparent 43 Polycarbonatediol Colorless andTerminal modified transparent 44 Polycarbonatediol Colorless andTerminal modified transparent

The viscosity of the functional filler composition solution in which thesurface of the filler was treated with poly-D-lactic acid orpoly-L-lactic acid had higher viscosity than that of the melt product ofpoly-L-lactic acid or poly-D-lactic acid polymerized in a similarcondition except without adding a filler.

In the case of using an organic filler such as pentaerythritol as theraw material filler (Sample 11, or the like), since the organic filleritself had a size at the molecular level, the reaction proceededeffectively by sufficiently dispersing D-lactic acid, and the functionalfiller composition became transparent. On the other hand, in the statethat the raw material organic filler such as trimesic acid hadcrystallinity and was a solid form and was not sufficiently dispersedinto D-lactic acid, the raw material organic filler with a largeparticle form remained and the functional filler composition appeared tobe non-transparent. Further, most of the functional fillers in which theorganic filler was used as the raw material filler were colorless andtransparent, and only the functional filler in which the surface wasaminated was yellow.

Test Example 1 Confirmation of Bonding of the Raw Material Filler andPolylactic Acid

1) IR was measured on Sample 28 and a raw material filler thereof,1,4-phenylenediamine, using an IR measurement apparatus (MAGNA-IR760)manufactured by Nicoler Instrument Cooperation. The result is shown inFIG. 2.

As shown in FIG. 2, a peak by aromatic amine clearly appears in thechart of 1,4-phenylenedimaine which is the raw material filler. On theother hand, the peak by an amino group disappears in the chart of Sample28, and instead, a peak by an ester group clearly appears. Therefore, itwas proved that poly-D-lactic acid was bonded to both ends of1,4-phenyleneamine in Sample 28.

2) NMR was measured on Sample 24 and a raw material filler thereof,3-glycidoxypropyltrialkoxysilane, using an NMR measurement apparatus(JMM GSX270) manufactured by JEOL, Ltd. The result is shown in FIG. 3.

As shown in FIG. 3, a peak by a methoxy group and an epoxy group clearlyappears in the chart of 3-glycidoxypropyltrialkoxysilane. On the otherhand, the peak by the methoxy group and the epoxy group disappears inthe chart of Sample 24, and instead, a peak by poly-D-lactic acidappears. Therefore, it was proved that poly-D-lactic acid was bonded toboth ends of 3-glycidoxypropyltrialkoxysilane in Sample 24.

Production Example 2 Production of Resin Composition Using FunctionalFiller Composition

The functional filler compositions 1 to 14 in which the surface wastreated with poly-D-lactic acid or poly-L-lactic acid, obtained inProduction Example 1, were melted and kneaded with a homo-poly-L-lacticacid (weight average molecular weight: 200,000, Tm=170° C.) as a matrix,at 190° C. for 15 minutes with a laboratory kneader mill so that theweight ratio of the former: the later was 1:10, thereby to obtain aresin composition in which the functional filler was homogenouslydispersed. The resin compositions were made into a pellet and used in astructure analysis, or the like.

Test Example 2 Evaluation of the Thermal Characteristics

The resin compositions obtained in Production Example 2 were heated, andbehaviors thereof were observed. The results are shown in Table 2.

TABLE 2 Functional filler composition Sample number Raw material fillerTg (° C.) Tc (° C.) Tm1 (° C.) Tm2 (° C.) No filler (only — 58 115 172 —polylactic acid) 1, 2, 3 Surface-aminated — — 170 216 silica 4Nanosilica — — 170 216 5 Surface-epoxylated — — 170 216 silica 6 KunipiaP — — 170 216 7 Aerosil silica — — 170 216 8 Aerosil silica 58 115 170 —9 Linear hydroxyapatite — — 170 216 11, 12 Pentaerythritol — — 170 21613  Trimesic acid — — 170 216 14  Dipentaerythritol — — 170 216

As shown in Table 2, the compositions in which the resin compositioncontaining a functional filler treated with poly-D-lactic acid wasmelted and kneaded with poly-L-lactic acid other than Sample 8 do notshow a clear Tg and Tc. Further, the compositions showed a melting pointTm by a homo-poly-L-lactic acid of a matrix polymer around 170° C., andshowed a melting point Tm2 considered to be due to a stereo complexformed from poly-L-lactic acid and poly-D-lactic acid around 216° C. Onthe other hand, the resin composition of sample number 8 containing thefunctional filler treated with poly-L-lactic acid shows a clear Tg andTc, and does not have the melting point Tm2 by stereo complex.

An increase of a crystallization speed after molding and improvement ofheat resistance become possible by molding the resin compositioncontaining the functional filler treated with poly-D-lactic acid betweentwo melting points. In detail, in the case of molding the resincomposition of the present invention at a temperature between twomelting points, poly-lactic acid itself melts, and on the other hand,the stereo complex of the functional filler with polylactic acid doesnot melt. As a result, since the stereo complex is a crystal at molding,the stereo complex becomes a nucleus at cooling after molding andpromotes crystallization of polylactic acid. Further, since manystereocomplexes exist as a nucleus, many crystals with a relativelysmall size are produced after cooling, and the heat resistance isimproved.

As described above, the resin composition of the present invention isfound to have characteristics of having a good moldability and also goodheat resistance.

Test Example 3 Evaluation of Moldability and Physical Properties of theResin Composition Containing the Functional Filler

The resin compositions obtained in Production Example 2 was molded intosheets having 0.2 mm thickness by hot-pressing at 190° C. under pressureof 30 MPa for 3 minutes, and then rapidly cooling with cold pressing.Heat treatment was further performed on the sheets at 130° C. for 1 hourin order to complete the crystallization.

The transparencies of these sheets were evaluated by lighttransmittance. The result is shown in Table 3.

TABLE 3 Functional filler composition Rapidly Heat Sample Raw materialcooled treated number filler sheet sheet Notes No filler — Transparent,Non-transparent, Crystal size (only colorless white large polylacticacid) 1, 2, 3 Surface- Transparent, Transparent, Crystal size aminatedyellow yellow small silica 4 Nanosilica Transparent, Transparent,Crystal size colorless colorless small 5 Surface- Transparent,Transparent, Crystal size epoxylated colorless colorless small silica 6Kunipia P Transparent, Non-transparent, Crystal size yellow yellow large7 Aerosil silica Transparent, Transparent, Crystal size colorlesscolorless small 8 Aerosil silica Transparent, Non-transparent, Crystalsize colorless white large 9 Linear Non-transparent, Non-transparent,Crystal size hydroxyapatite white white small, filler size large 11, 12Pentaerythritol Transparent, Transparent, Crystal size colorlesscolorless small 13  Trimesic acid Non-transparent, Non-transparent,Dispersibility of white white trimesic acid was poor 14 Dipentaerythritol Transparent, Transparent, Crystal size colorlesscolorless small

As the result described in Table 3, in the case of not containing thefunctional filler of the present invention, the rapidly cooled sheet wastransparent. However, the heat treated sheet became white andnon-transparent. This showed that a large spherical-shaped crystal ofpolylactic acid was formed by crystallization. Therefore, theconventional sheet becomes very brittle in the aspect of physicalproperties and is inappropriate in practical use, since there is nobonding force between domains of the large spherical-shaped crystalsalthough it has regular heat resistance in addition to thenon-transparent properties. In the case that the raw material filler wassurface-epoxylated silica, surface-aminated silica, nanosilica orAEROSIL SILICA (Sample 8 treated with poly-L-lactic acid was excluded),any of the rapidly cooled sheet and the heat treated sheet maintainedtransparency, and it was shown that the size of the crystallizedspherical-shaped crystal produced was finer than the size of lightwavelength.

It was found that the dispersibility of the filler in the resincomposition in which the functional filler composition havingmontmorillonite (manufactured by Kunimine Industries Co., Ltd., KunipiaP) as the raw material filler was remarkably improved. However,whitening due to the heat treatment showed that the size of the producedspherical-shaped crystal by the heat treatment became large. Further, inthe case that fibrous hydroxyapatite was used as the raw materialfiller, it was considered that a composite became non-transparent sincethe particle size of fibrous hydroxyapatite was large.

Moreover, crystallinity of the heat treated sheet can be evaluated withDSC, and for any of the sheets, a melting point Tm1 of poly-L-lacticacid was observed around 170° C. and a melting point Tm2 due to a stereocomplex formed from poly-L-lactic acid and poly-D-lactic acid wasobserved around 216° C. Therefore, the resin composition is excellent inmoldability and heat resistance.

Test Example 4 Evaluation of Heat Resistance

Evaluation of the heat resistance of the sheet was performed with theheat sag test described above, and the heat resistance was evaluated byhow much the tip of the sheet was lowered from the horizon after theheat treatment according JIS K7195. When the distance of lowering wasless than 10 mm, the sheet was shown to be thermally stable at thistemperature. The result in which the sheets were treated at 130° C. forone hour is shown in Table 4.

TABLE 4 Deformation amount and heat resistance evaluation Rapidly cooledHeat treated Functional filler sheet sheet composition Heat Heat SampleRaw material Deformed resist- Deformed resist- number filler amount anceamount ance No filler — >50 mm Poor <10 mm Good (only polylactic acid)1, 2, 3 Surface- <10 mm Good <10 mm Good aminated silica 4 Nanosilica<10 mm Good <10 mm Good 5 Surface- <10 mm Good <10 mm Good epoxylatedsilica 6 Kunipia P <10 mm Good <10 mm Good 7 Aerosil silica <10 mm Good<10 mm Good 8 Aerosil silica >50 mm Poor <10 mm Good 9 Linear <10 mmGood <10 mm Good hydroxyapatite 11, 12 Pentaerythritol <10 mm Good <10mm Good 13  Trimesic acid <10 mm Good <10 mm Good 14  Dipentaerythritol<10 mm Good <10 mm Good

The rapidly cooled sheet without a filler and the rapidly cooled sheetin which the functional filler composition of Sample 8 was blended weredeformed right away at 130° C., and showed a large deformed amount. Thiswas considered to be because, since Tg was around 60° C. when onlyhomo-polylactic acid was included, the sheet was easily deformed at thattemperature or more. The sheet without a filler treated at 130° C. forone hour had heat resistance. However, the sheet was non-transparent.

On the other hand, the heat resistance of any of the resin compositionsof the present invention (one in which the functional filler compositionof Sample 8 was blended was excluded) was excellent. This was consideredto be because the resin compositions of the present invention did nothave a clear Tg as a result in the above-described Test Example 2.

Production Example 3 Production of Pellet

Pellets were produced using the functional filler of the presentinvention, as a material of various molded bodies. Specifically, thefunctional filler and the matrix poly-L-lactic acid were kneaded at aratio of functional filler:poly-L-lactic acid=1:9 using a biaxialextruder (manufactured by Technovel Cooperation, KZW15-30MG:L/D). Atthat time, the cylinder temperature was set to 180° C. and the dietemperature was set to 173° C., and a strand was cut directly with apelletizer to obtain a pellet with 2 to 3 cm length. The thermalcharacteristics of the obtained pellet are as follows.

TABLE 5 Thermal Sample characteristics of number Raw material filler TgTc Tm1 Tm2 12 Pentaerythritol — — 168 203.9 22 PEG 600 — — 170 205.2 23Tetraethoxysilane — — 170 200.0 24 Methylethoxysilane — — 170 185.6 25Sila-ace S330 — — 170 189.8 26 Sila-ace S510 — — 170 192.8 27 Melamine —— 170 211.8 28 Silaplane FMDA11 — — 170 203.9 29 Silaplane FM3311 — —170 205.8 30 Phenylenediamine — — 170 190.5 31 Hexamethylenediamine — —170 195.7 34 4,4′-biphenol — — 170 200.6 35 Zirconium tetrapropoxide — —170 201.7 36 1,3,5-tris(2-hydroxy- — — 170 202.3 ethyl)cyanuric acid 37N,N′-bis(hydroxy- — — 170 199.3 ethyl)oxide 38 Bisphenol — — 170 210.539 Polycarbonatediol — — 170 205.4 40 Polycarbonatediol — — 170 203.5

Though the kneading temperature was a little better than the normalkneading temperature of polylactic acid, the stereo complex played arole of a nucleating agent when polylactic acid was extruded from anozzle. As a result, the extruded polylactic acid composite materialsolidified at room temperature, and could be directly cut withoutcooling with water. Compared with a homo-poly-L-lactic acid, it wasfound that the resin composition of the present invention had a meltingpoint of polylactic acid stereo complex between 190 and 210° C. otherthan the homo-polylactic acid melting point around 170° C. The stereocomplex part became large with the increase of the added amount of thefunctional filler, and a crystallized polylactic acid composition couldbe easily obtained.

The composite pellet produced in Production Example 3 was applied to thevarious molding methods as follows.

Production Example 4

A resin composition containing a functional filler having an organicsubstance as the raw material filler was selected in the resincompositions of the present invention prepared in Production Example 3,the functional filler content was changed, and the composition wasapplied to an injection molding. Specifically, the cylinder temperaturewas made to be the stereo complex melt temperature or more, and thenozzle temperature was made to be the stereo complex temperature orless. By making the cylinder temperature to be the stereo complex melttemperature or more, the functional filler-containing polylactic acidcomposite material was sufficiently melted in the cylinder, and mixedhomogenously. Further, by making the nozzle temperature to be the stereocomplex temperature or less, the injected stereo complex became solidright away. The mold temperature was set to 27° C., and the mold cyclewas set to 20 seconds. The impact strength of each molded body wasmeasured using Izod impact strength test machine manufactured by ToyoSeiki Kogyo Co., Ltd. according to JIS K7110. The result is shown inTable 6.

TABLE 6 Injection molding Filler temperature Raw content Cylinder DieImpact Molded Sample material (% by temperature temperature strengthproduct number filler mass) (° C.) (° C.) (KJ/m²) property 12Pentaerythritol 5 210 180 3.1 Transparent 10 2.8 22 PEG600 5 220 220 3.0Transparent 10 2.9 20 2.4 23 Tetraethoxysilane 5 210 200 3.4 Transparent10 3.1 24 Methyl- 5 210 200 2.8 Transparent triethoxysilane 10 2.9 25Sila-ace S330 5 210 200 2.8 Transparent 10 2.9 26 Sila-ace S510 5 210200 2.8 Transparent 10 2.9 27 Melamine 5 210 200 2.8 Transparent 10 2.928 Silaplane FMDA11 5 210 200 2.8 Transparent 10 2.9 29 Silaplane FM33115 210 200 2.8 Transparent 10 2.9 30 Phenylenediamine 5 210 200 2.8Transparent 10 2.9 31 Hexamethylene- 5 210 200 2.8 Transparent diamine10 2.9 34 4,4′-biphenol 5 210 200 3.2 Transparent 10 3.1 35 Zirconium 5210 200 3.0 Transparent tetrapropoxide 10 2.9 36 1,3,5-tris(2-hydroxy- 5210 200 3.5 Transparent ethyl)cyanuric acid 10 3.2 37 N,N′-bis(hydroxy-5 210 200 3.1 Transparent ethyl)oxide 10 2.8 38 Bisphenol 5 210 200 3.2Transparent 10 3.0 39 Polycarbonatediol 5 210 200 3.4 Transparent(UC-CARB100) 10 3.2 40 Polycarbonatediol 5 210 200 2.9 Transparent(UH-200) 10 2.8

The stereo complex formed with the functional filler of the presentinvention and polylactic acid became a nucleus of the crystal afterinjected, promoted solidification, shortened the molding cycle, and atthe same time, transparency of the molded body could be improved.

Further, the impact strength of the conventional homo-polylactic acid is2.6 KJ/m². On the other hand, the impact strength could be improved toabout 3.0 KJ/m² in case that the added amount of the functional fillerof the present invention was made to be 5 to 10% by mass as in theabove-described result. However, when the added amount of the functionalfiller was increased to 20% by mass, the impact strength ratherdecreased.

Production Example 5

A pellet containing the functional filler in which pentaerythritol andAEROSIL SILICA were made to be the raw material filler in the pelletsproduced in Production Example 3 was applied to a carbon dioxide foamingunder the following condition. The result is as follows.

TABLE 7 Foaming condition Raw Chamber Co₂ soaking material temperaturepressure Time filler (° C.) (MPa) (minute) Pentaerythritol  5 mass % 17020 240 10 mass % 170 20 240 20 mass % 170 20 240 30 mass % 170 20 240Aerosil silica  5 mass % 170 20 240 10 mass % 200 20 240 20 mass % 20020 240 30 mass % 200 20 240

By the formation of the stereo complex of the functional filler andpolylactic acid, the stereo complex was in a solid state even at themelting point of a normal polylactic acid or more, and the effect ofimproving the viscosity of polylactic acid was exhibited. Furthermore,with the existence of the stereo complex, the foamed polylactic acidmolded product was crystallized at a foaming step, and showed higherheat resistance than that of a non-crystalline polylactic acid foamedbody. In the view of the physical properties of one foamed by carbondioxide, a foam molding of even polylactic acid that hardly foamedbecame possible by adding a small amount of filler, the heat resistancethereof was 100° C. or more, and it was found that the molded productcould take the place of the PS foaming body used in everyday life.

Production Example 6

Melt-spinning of Sample 12 containing the functional filler in whichpentaerythritol was used as the raw material filler among the compositeproducts kneaded in Example 3 was performed in the following condition.

TABLE 8 Melt-spinning temperature Cylinder Die Raw material fillertemperature temperature Pentaerythritol (° C.) (° C.)  5 mass % 180 17010 mass % 180 170 20 mass % 180 170

The spinning of the resin composition of the present invention ispreferably performed at the melting point of homo-polylactic acid ormore and the melting point of the stereo complex or less. The reason isbecause the viscosity becomes considerably low when the stereo complexmay melt and become difficult to be molded product. Therefore, byspinning at the melting point of homo-polymer or more and the meltingpoint of the stereo complex or less, and with the stereo complexpartially forming, homo-polymers connect together, and an apparent longmolecular can be spun. In the present example, the spinning temperaturewas set to 170° C., and a multi-filament was obtained with amelt-spinning. Further, since there was not a change in the viscosity,the spinning could be performed without necessity of especiallyimproving the existing apparatus using the resin composition of thepresent invention.

Production Example 7

The pellet containing the functional filler in which dipentaerythritoland AEROSIL SILICA were used as the raw material filler among thepellets produced in Production Example 3 was formed into a sheet.

TABLE 9 Sheet molding temperature Cylinder Heat properties of T dietemper- T die extruding molded product Polymerization ature temperatureTg Tc1 Tm1 Tm2 initiator (° C.) (° C.) (° C.) (° C.) (° C.) (° C.)Dipentaerythritol 20 mass % 180 170 53.7  99.1 162.3 210 30 mass % 180170 55.9 109.6 164.3 210.3 Aerosil silica (1:10) 30 mass % 190 180 54.2— 164.5 211.6

As the above-described result, in the case that the added amount of thefunctional filler was large, the molded sheet started having heatresistance from the point when the molded came out from T die. Such heatresistance was considered to be obtained by that it became easily to becrystallized due to the stereo complex and that mobility of thepolylactic acid molecule was restricted. The polylactic sheet releasedfrom the T die had both transparency and heat resistance, and asecondary process was also possible.

Production Example 8

Spinning of a mono-filament was performed using the resin composition ofSample 39 containing the functional filler in which pentaerythritol wasused as the raw material filler and the ends thereof were treated withacetic anhydride. Specifically, the resin composition was melted at 170to 190° C. with a mono-axial melt-extruder to be ejected from aspinneret of 1.2 mm diameter, and passed in warm water of 60° C. througha gap of 50 mm. In the warm water, the composition was solidified whilesufficient tension was kept, and 5-times stretching was performed in hotwater of 90° C. Furthermore, 2-times stretching was performed insuperheated steam of 130° C. Then, a mono-filament was obtained byperforming a heat treatment while the length was kept in air of 150 to180° C. The obtained mono-filament was transparent and flexible, and hada fineness of 300 dTex. Further, the strength of the filament wasmeasured. As a result, the filament had extremely high strength for amono-filament as the maximum strength being 600 MPa and the elongationat break being 33%.

Production Example 9

AEROSIL SILICA A300 (manufactured by Nippon Aerosil Co., Ltd., aspherical silica having average particle size 30 nm, 56 parts by mass)was dispersed into ethanol (2000 parts by mass) in which water (100parts by mass) was added, 3-aminopropyltriethoxysilane (20 parts bymass) was added, and the mixture was stirred at room temperature for 24hours. Surface-aminated silica (60 parts by mass) was obtained byfiltering the silica particle at a reduced pressure, cleaning withethanol, and drying at 100° C.

Subsequently, the surface-aminated silica (50 parts by mass) wasdispersed into D-lactic acid (manufactured by PURAC, 90% by mass, 550parts by mass) in a 1 L four-necked flask, and then the resultingmixture was stirred for 24 hours at 140° C. under argon bubbling toperform dehydration polymerization. Progress of the polymerizationreaction was confirmed with the amount of the produced water. After thecompletion of the reaction, a viscous liquid product which was slightlyyellowish and transparent was obtained. The obtained functional fillercomposition was almost transparent, and this showed that the silicaparticles were almost completely dispersed into poly-D-lactic acid. Thereaction product was extruded in a strand shape under the flask, cut,and made into a pellet. The above-described functional fillercomposition consisted of silica nano-particles of 11% by mass andpoly-D-lactic acid of 89% by mass. As the result of the GPC measurement,the weight average molecular weight (Mw) of poly-D-lactic acid that didnot bond to the filler was 3300. The present functional filler (10% bymass) was dry-blended with poly-L-lactic acid (melting point: 173° C.,weight average molecular weight: 180,000, 90% by mass), melted andkneaded at 180 to 200° C. using a biaxial kneader, and then the resincomposition was obtained by making it into a pellet by air cooling.

The spinning of a mono-filament was performed as below using the resincomposition. The resin composition was melted at 170 to 190° C. andejected from a spinneret of 1.2 mm diameter with a mono-axialmelt-extruder, and passed in warm water of 60° C. through a gap of 50mm. In the warm water, the composition was solidified while sufficienttension was kept, and 5-times stretching was performed in hot water of90° C. Furthermore, 2-times stretching was performed in superheatedsteam of 130° C. Then, a transparent and flexible mono-filament of 350dTex having a hardness was obtained by performing a heat treatment at aconstant length in air of 150 to 180° C. The obtained mono-filament waspolylactic acid fiber having extremely excellent physical propertieswith the maximum strength of 610 MPa and the elongation at break being36%.

Production Example 10

A multi-filament was produced using the resin composition of Sample 41containing the functional filler in which polyethylene glycol (molecularweight 600) was used as the raw material filler and the ends thereof wastreated with acetic anhydride. Specifically, a non-stretched yarn wasobtained by extruding the resin composition from a spinneret having 32pores of pore diameter 0.25 mm into air to be solidified, and winding at800 m/minute. Then, the non-stretched yarn was stretched 5-times with ahot roller of 95° C., and further stretched 2.5-times with a hot rollerat 135° C. Next, a multi-filament of 75 dTex/32 fil was obtained byperforming a heat treatment by contacting a hot plate at 150° C. whilethe length was kept. The maximum strength of the multi-filament was 780MPa, the initial modulus of elasticity was 10500 MPa (10.5 GPa), and theelongation at break was 43%. According to the a result, it was provedthat a multi-filament having excellent physical properties could beobtained by using the resin composition of the present invention as araw material.

Production Example 11

A semi-stretched yarn was obtained by using the same resin compositionas Production Example 10 and spinning at 3000 m/minute. Thissemi-stretched yarn was stretched 5-times with a heat roller having asurface temperature of 120° C., and further stretched 3-times with aheat roller having a surface temperature at 135° C. Then, amulti-filament of 50 dTex/32fil was obtained by performing a heattreatment by contacting the stretched yarn with a hot plate of 150° C.while the length was kept. The maximum strength of the multi-filamentwas 1.30 GPa, the initial modulus of elasticity was 16 GPa, and theelongation at break was 29%. According to the result, it was proved thata multi-filament having high strength and high modulus of elasticity ata level that had never been reported could be obtained by using theresin composition of the present invention as a raw material.

Production Example 12

Pentaerythritol (13.6 parts) and 90% of D-lactic acid solution (2000parts) were mixed, reacted for 24 hours at 140° C. under argon bubbling,and further reacted for 24 hours at 170° C. As a result, 1430 parts ofthe functional filler in which poly-D-lactic acid was bonded to fourhydroxide group ends of pentaerythritol was obtained. The functionalfiller and poly-L-lactic acid (melting point=165° C., Mw=185,000) weremixed at a ratio of 5:95 in a mass conversion. The mixture was suppliedin a single axial kneader having an inflation spinneret, kneaded andmelted at a temperature of 170 to 190° C., and extruded into air withthe usual method from a circular spinneret set at 180 to 190° C. Afterbeing extruded, the mixture was blown to three times with air pressure.After blowing, the mixture was molded into a sheet of 15 mm widththrough a slitter right away. Then, the sheet was primary stretched4-times in the longitudinal direction with a plate heater with a surfacetemperature 120° C. Furthermore, the primary stretched tape wassecondary stretched 2.5 times with a plate heater with a surfacetemperature of 140° C. A flat yarn of 600 dTex was obtained byperforming a heat treatment on the secondary stretched tape at aconstant length with a heater with a surface temperature of 150° C. Thetensile strength of the flat yarn was 5.6 cN/dTex, the tensileelongation at break was 27%, and the hot water shrinkage rate was 1.6%.

For comparison, production of a flat yarn was attempted only withpoly-L-lactic acid in a similar way as described above except that thefunctional filler of the present invention was not used. However, thetape was easily melted and broke with heat at the primary stretching, astretching spot was generated by local heat, and good stretching couldnot be performed. Further, production of a flat yarn was attempted onlywith poly-D-lactic acid having large molecular weight in a similar wayas described above except that the functional filler of the presentinvention was not used. As a result, the blow film itself was verybrittle, the formation of balloons was difficult, and even the formationof a sheet could not be performed.

Production Example 13

Polyethylene glycol 600 (manufactured by Kanto Chemical Co., Inc.,PEG-600, 100 parts) and 90% of D-lactic acid aqueous solution (1000parts) were mixed, reacted for 24 hours at 140° C. under argon bubbling,and further reacted for 24 hours at 170° C. As a result, 750 parts ofthe functional filler in which poly-D-lactic acid was bonded to two OHgroup ends of PEG-600 was obtained. The functional filler andpoly-L-lactic acid (melting point=165° C., Mw=185,000) were mixed at aratio of 7.5:92.5 in a mass conversion. The mixture was supplied in asingle axial kneader having an inflation spinneret, kneaded and meltedat a temperature of 165 to 180° C., and extruded into air with the usualmethod from a circular spinneret set at 170 to 180° C. After beingextruded, the mixture was blown to 2.5 times lengthwise and 2 timescrosswise with air pressure, and made into a film of 30 μm thickness.The film was folded in two with a usual method, and wound in a tubeshape.

The physical properties of the obtained tube were measured with DSC. Asa result, a melting peak of polylactic acid was confirmed at around 170°C., and about 1 to 2 melting peaks of the complex of poly-L-lactic acidconstituting a matrix with poly-D-lactic acid originated from thefunctional filler were confirmed at around 190 to 200° C.

For comparison, a similar film was produced only with polylactic acidwithout using the functional filler of the present invention. As aresult of measuring the obtained film with DSC, a crystallization peakof polylactic acid was confirmed at around 100° C., and a melting peakwas confirmed at around 170° C. From this result of DSC, it was foundthat the degree of crystallization of the film increased and the heatresistance of the obtained film was improved by adding the functionalfiller of the present invention.

INDUSTRIAL APPLICABILITY

The realization of the following cases become possible with the presentinvention.

1. Homogenous dispersibility of the filler for a liquid, a polymer orthe like as a matrix can be improved. Therefore, the development ofvarious additives, nucleating agents, reinforcing materials andlubricants which are excellent in various physical properties becomespossible.

2. Physical properties such as strength and moldability of polylacticacid composition can be improved.

3. Heat resistance and mechanical strength of a pellet, a sheet, a film,an injection-molded body, an extrusion-molded body, an inflation film, afiber or the like and other application products including polylacticacid as the main component can be improved.

1-13. (canceled)
 14. A method for producing a functional filler,comprising the steps of: mixing a solution or melt of D-lactic acid orL-lactic acid and/or D-lactide or L-lactide with a silicon-basedalkoxide; and polymerizing the lactic acid and/or lactide to modify thesilicon-based alkoxide with the poly-D-lactic acid or the poly-L-lacticacid.
 15. The method according to claim 14, wherein an excessive amountof the D lactic acid or L-lactic acid and/or D-lactide or L-lactide ismixed with the silicon-based alkoxide during mixing the solution or meltwith the silicon-based alkoxide.
 16. The method according to claim 14,further comprising the step of: mixing the silicon-based alkoxidemodified by poly-D-lactic acid or the poly-L-lactic acid with thepolylactic acid as a matrix polymer at least partly interacting with thepoly-D-lactic acid or the poly-L-lactic acid modifying the silicon-basedalkoxide.
 17. (canceled)